Systems, methods, and apparatuses related to vehicles with reduced emissions

ABSTRACT

This disclosure relates generally to vehicles with reduced emissions. More particularly, this disclosure relates to systems, methods, and apparatuses related to vehicles with reduced carbon dioxide emissions. The carbon dioxide emissions may be stored in a carbon dioxide clathrate.

If an Application Data Sheet (ADS) has been filed on the filing date ofthis application, it is incorporated by reference herein. Anyapplications claimed on the ADS for priority under 35 U.S.C. §§119, 120,121, or 365(c), and any and all parent, grandparent, great-grandparent,etc. applications of such applications, are also incorporated byreference, including any priority claims made in those applications andany material incorporated by reference, to the extent such subjectmatter is not inconsistent herewith.

1. CROSS-REFERENCE TO RELATED APPLICATIONS

The present application is related to and/or claims the benefit of theearliest available effective filing date(s) from the following listedapplication(s) (the “Priority Applications”), if any, listed below(e.g., claims earliest available priority dates for other thanprovisional patent applications or claims benefits under 35 USC §119(e)for provisional patent applications, for any and all parent,grandparent, great-grandparent, etc. applications of the PriorityApplication(s)). In addition, the present application is related to the“Related Applications,” if any, listed below.

2. PRIORITY APPLICATIONS

None

3. RELATED APPLICATIONS

U.S. patent application Ser. No. 13/957,083, entitled SYSTEMS, METHODS,AND APPARATUSES RELATED TO VEHICLES WITH REDUCED EMISSIONS, namingRoderick A. Hyde and Lowell L. Wood, Jr. as inventors, filed Aug. 1,2013, is related to the present application.

U.S. patent application Ser. No. 13/957,114, entitled SYSTEMS, METHODS,AND APPARATUSES RELATED TO VEHICLES WITH REDUCED EMISSIONS, namingRoderick A. Hyde and Lowell L. Wood, Jr. as inventors, filed Aug. 1,2013, is related to the present application.

U.S. patent application Ser. No. 13/957,118, entitled SYSTEMS, METHODS,AND APPARATUSES RELATED TO VEHICLES WITH REDUCED EMISSIONS, namingRoderick A. Hyde and Lowell L. Wood, Jr. as inventors, filed Aug. 1,2013, is related to the present application.

The United States Patent Office (USPTO) has published a notice to theeffect that the USPTO's computer programs require that patent applicantsreference both a serial number and indicate whether an application is acontinuation, continuation-in-part, or divisional of a parentapplication. Stephen G. Kunin, Benefit of Prior-Filed application, USPTOOfficial Gazette Mar. 18, 2003. The USPTO further has provided forms forthe Application Data Sheet which allow automatic loading ofbibliographic data but which require identification of each applicationas a continuation, continuation-in-part, or divisional of a parentapplication. The present Applicant Entity (hereinafter “Applicant”) hasprovided above a specific reference to the application(s) from whichpriority is being claimed as recited by statute. Applicant understandsthat the statute is unambiguous in its specific reference language anddoes not require either a serial number or any characterization, such as“continuation” or “continuation-in-part,” for claiming priority to U.S.patent applications. Notwithstanding the foregoing, Applicantunderstands that the USPTO's computer programs have certain data entryrequirements, and hence Applicant has provided designation(s) of arelationship between the present application and its parentapplication(s) as set forth above and in any ADS filed in thisapplication, but expressly points out that such designation(s) are notto be construed in any way as any type of commentary and/or admission asto whether or not the present application contains any new matter inaddition to the matter of its parent application(s).

If the listings of applications provided above are inconsistent with thelistings provided via an ADS, it is the intent of the Applicant to claimpriority to each application that appears in the Priority Applicationssection of the ADS and to each application that appears in the PriorityApplications section of this application.

All subject matter of the Priority Applications and the RelatedApplications and of any and all parent, grandparent, great-grandparent,etc. applications of the Priority Applications and the RelatedApplications, including any priority claims, is incorporated herein byreference to the extent such subject matter is not inconsistentherewith.

TECHNICAL FIELD

This disclosure relates generally to vehicles with reduced emissions.More particularly, this disclosure relates to systems, methods, andapparatuses related to vehicles with reduced carbon dioxide emissions.

SUMMARY

This disclosure provides methods of sequestering emissions. A firstmethod may comprise operating an engine of a vehicle and then combiningcarbon dioxide from an exhaust stream of the engine with a hostmaterial, and wherein the host material is compatible with formingcarbon dioxide clathrates with the carbon dioxide of the exhaust stream.The first method may further comprise pressurizing and cooling theexhaust stream and host material sufficient to form carbon dioxideclathrates with the carbon dioxide and the host material. The firstmethod may also further comprise storing formed carbon dioxideclathrates in an exhaust storage vessel of the vehicle during operationof the engine.

A second method may comprise storing gas clathrates in a clathratestorage vessel, separating stored gas clathrates into at least one gasand a host material, and operating an engine of a vehicle utilizing theat least one gas as fuel. The second method may further comprisecombining carbon dioxide from an exhaust stream of the engine with hostmaterial, wherein the host material is compatible with forming carbondioxide clathrates with the carbon dioxide of the exhaust stream. Thesecond method may further comprise pressurizing and cooling the exhauststream and the host material sufficient to form carbon dioxideclathrates with the carbon dioxide and the host material. The secondmethod may also further comprise storing formed carbon dioxideclathrates in the clathrate storage vessel during operation of theengine.

A third method may comprise storing fuel as a liquid or gas andoperating an engine of a vehicle using the fuel. The third method mayfurther comprise combining an exhaust stream of the engine with a hostmaterial, wherein the exhaust stream comprises carbon dioxide andwherein the host material is compatible with forming carbon dioxideclathrates with the carbon dioxide of the exhaust stream. The thirdmethod may further comprise pressurizing and cooling the exhaust streamand host material sufficient to form carbon dioxide clathrates with thecarbon dioxide and the host material. The third method may furthercomprise storing formed carbon dioxide clathrates in an exhaust storagevessel of the vehicle during operation of the engine.

This disclosure also provides vehicles with reduced emissions. In someembodiments, the vehicle comprises a separation system operablyconnected to the fuel storage vessel and configured to dissociate thegas clathrates into a host material and at least one gas. The vehiclemay further comprise an engine operably connected to the separationsystem and configured to utilize the at least one gas as fuel. Thevehicle may additionally comprise a clathrate formation system operablyconnected to the engine and configured to combine carbon dioxide from anexhaust stream from the engine with host material to form carbon dioxideclathrates. The vehicle may further comprise an exhaust storage vesseloperably connected to the clathrate formation system and configured tostore carbon dioxide clathrates.

In some embodiments, the vehicle comprises a clathrate storage vesselconfigured to store gas clathrates and carbon dioxide clathrates. Thevehicle may further comprise a separation system configured todissociate the gas clathrates into a host material and at least one gasand an engine configured to utilize the at least one gas as fuel. Thevehicle may further comprise a clathrate formation system configured tocombine carbon dioxide from an exhaust stream from the engine, with hostmaterial to form carbon dioxide clathrates.

In some embodiments, the vehicle comprises an engine, a supply of hostmaterial, and a clathrate formation system operably connected to theengine, operably connected to the supply of host material, andconfigured to combine carbon dioxide from an exhaust stream from theengine with the host material to form carbon dioxide clathrates. Thevehicle may further comprise an exhaust storage vessel configured tostore carbon dioxide clathrates.

In some embodiments, the vehicle comprises a clathrate storage vesselconfigured to store gas clathrates at a first temperature and a firstpressure and an engine operably connected to the clathrate storagevessel and configured to receive discharged at least one gas from theclathrate storage vessel. The vehicle may further comprise an exhaustdelivery system operably connected to the engine and configured tointroduce carbon dioxide from an exhaust stream from the engine into theclathrate storage vessel at a temperature and pressure substantially thesame as the first temperature and pressure. The clathrate storage vesselmay be configured to discharge the at least one gas and store carbondioxide clathrates.

In some embodiments, the vehicle comprises a fuel storage vesselconfigured to store gas clathrates and an exchange vessel operablyconnected to the fuel storage vessel and configured to receive the gasclathrates. The exchange vessel may be configured to maintain the gasclathrates at a first temperature and a first pressure and may beconfigured to exchange carbon dioxide for at least one gas within thegas clathrates. The exchange vessel may be configured to discharge theat least one gas and carbon dioxide clathrates. The vehicle may furthercomprise an engine operably connected to the exchange vessel andconfigured to receive discharged gas from the exchange vessel. Thevehicle may further comprise an exhaust delivery system operablyconnected to the engine and configured to introduce carbon dioxide froman exhaust stream from the engine into the exchange vessel at atemperature and pressure substantially the same as the first temperatureand pressure. The vehicle may further comprise an exhaust storage vesselconfigured to receive the carbon dioxide clathrates from the exchangevessel.

This disclosure also provides kits for reducing the emissions ofexisting vehicles. The kits may comprise a host material storage vesseland a clathrate formation system configured for operable connection toan engine of a vehicle, configured to be operably connected to the hostmaterial storage vessel, and configured to combine an exhaust streamfrom the engine with host material to form carbon dioxide clathrates.The kits may further comprise an exhaust storage vessel configured tostore carbon dioxide clathrates.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates an embodiment of a vehicle configured to sequestercarbon dioxide emissions.

FIG. 2 illustrates another embodiment of a vehicle configured tosequester carbon dioxide emissions.

FIG. 3 illustrates another embodiment of a vehicle configured tosequester carbon dioxide emissions.

FIG. 4 illustrates another embodiment of a vehicle configured tosequester carbon dioxide emissions.

FIG. 5 illustrates another embodiment of a vehicle configured tosequester carbon dioxide emissions.

DETAILED DESCRIPTION

Natural gas is a cleaner-burning fuel compared to traditional fossilfuels. However, natural gas at ambient temperatures and atmosphericpressure is a high-volume gas. For an automobile to store a sufficientamount of natural gas for operation comparable to that of a gasoline ordiesel engine, it has been necessary to increase the density of thenatural gas. One approach has been to liquefy the natural gas by coolingthe natural gas to about −162 degrees Centigrade. At that temperature,natural gas is a liquid at essentially ambient pressure. Storage ofliquid natural gas (LNG) requires the use of special cryogenicequipment. Another approach has been to compress the natural gas to apressure of about 200 to 248 bars. At that pressure and ambienttemperature, natural gas occupies about 1/100th the volume of naturalgas at general ambient temperatures and pressures. Storage of compressednatural gas (CNG) requires the use of high-pressure storage vessels.

Gas clathrates are chemical substances in which certain gas moleculesare trapped in a cage or crystal lattice formed by certain hostmaterials. In many cases, the gas molecules stabilize the crystallattice or cage, such that the crystal lattice or cage may maintain itsstructure at a much higher temperature and lower pressure than would bepossible without the presence of the gas molecules. Methane clathrates,for example, exist in nature, among other places, under sediments on theocean floors. Gas clathrates may be able to store gases, such asmethane, at volumes comparable to CNG, but at much lower pressures andat much higher temperatures than LNG.

Clathrates can also be formed with carbon dioxide. Carbon dioxideclathrates can be formed at temperatures and pressures similar to thosethat form gas clathrates and with similar host materials.

Combustion of gas clathrates refers to dissociation of gas(es) from theclathrate host material and then combustion of the gas(es). During theprocess of combustion of the gas(es) the host material may also bevaporized. This vaporization does not constitute combustion. However, insome embodiments, the host material may include elements that may becombustible under certain conditions. Dissociation of gas(es) from theclathrate host material includes any process for separating the gas(es)from the clathrate host material. This includes diffusion of the gas(es)away from the solid clathrate host material and/or melting of theclathrate host material to release the gas(es).

The phrases “operably connected to,” “connected to,” and “coupled to”refer to any form of interaction between two or more entities, includingmechanical, electrical, magnetic, electromagnetic, fluid, and thermalinteraction. Likewise, “fluidically connected to” refers to any form offluidic interaction between two or more entities. Two entities mayinteract with each other even though they are not in direct contact witheach other. For example, two entities may interact with each otherthrough an intermediate entity.

The term “substantially” is used herein to mean almost and including100%, including at least about 80%, at least about 90%, at least about91%, at least about 92%, at least about 93%, at least about 94%, atleast about 95%, at least about 96%, at least about 97%, at least about98%, and at least about 99%.

This disclosure provides methods of sequestering emissions. A firstmethod may comprise operating an engine of a vehicle and then combiningcarbon dioxide from an exhaust stream of the engine with a hostmaterial, and wherein the host material is compatible with formingcarbon dioxide clathrates with the carbon dioxide of the exhaust stream.The first method may further comprise pressurizing and cooling theexhaust stream and host material sufficient to form carbon dioxideclathrates with the carbon dioxide and the host material. The firstmethod may also further comprise storing formed carbon dioxideclathrates in an exhaust storage vessel of the vehicle during operationof the engine.

A second method may comprise storing gas clathrates in a clathratestorage vessel, separating stored gas clathrates into at least one gasand a host material, and operating an engine of a vehicle utilizing theat least one gas as fuel. The second method may further comprisecombining carbon dioxide from an exhaust stream of the engine with hostmaterial, wherein the host material is compatible with forming carbondioxide clathrates with the carbon dioxide of the exhaust stream. Thesecond method may further comprise pressurizing and cooling the exhauststream and the host material sufficient to form carbon dioxideclathrates with the carbon dioxide and the host material. The secondmethod may also further comprise storing formed carbon dioxideclathrates in the clathrate storage vessel during operation of theengine.

A third method may comprise storing fuel as a liquid or gas andoperating an engine of a vehicle using the fuel. The third method mayfurther comprise combining an exhaust stream of the engine with a hostmaterial, wherein the exhaust stream comprises carbon dioxide andwherein the host material is compatible with forming carbon dioxideclathrates with the carbon dioxide of the exhaust stream. The thirdmethod may further comprise pressurizing and cooling the exhaust streamand host material sufficient to form carbon dioxide clathrates with thecarbon dioxide and the host material. The third method may furthercomprise storing formed carbon dioxide clathrates in an exhaust storagevessel of the vehicle during operation of the engine.

The methods may further comprise removing stored carbon dioxide from thevehicle when the vehicle is otherwise not in use. The methods mayfurther comprise reporting the amount of carbon dioxide removed from thevehicle. By way of non-limiting example, the reporting may comprisedisplaying the amount of carbon dioxide removed from the vehicle in alocation visible to an operator of the vehicle. By way of non-limitingexample, the reporting may comprise wirelessly reporting the amount ofcarbon dioxide removed from the vehicle to an external agency. Likewise,the methods may further comprise reporting the ratio of carbon dioxideremoved from the vehicle to carbon dioxide produced by the engine. Byway of non-limiting example, the reporting may comprise displaying theratio of carbon dioxide removed from the vehicle to carbon dioxideproduced by the engine in a location visible to an operator of thevehicle. By way of non-limiting example, the reporting may comprisewirelessly reporting the ratio of carbon dioxide removed from thevehicle to carbon dioxide produced by the engine to an external agency.

In some embodiments of the first and third methods, removing storedcarbon dioxide from the vehicle comprises reducing the pressure and/orincreasing the temperature of the exhaust storage vessel sufficient todissociate the carbon dioxide clathrates stored therein back into carbondioxide and host material and venting gaseous carbon dioxide from theexhaust storage vessel. For example, the exhaust storage vessel may bewarmed sufficient to liquefy the host material and gasify the carbondioxide for venting. Heat to warm the exhaust storage vessel may come atleast partially from a source external to the vehicle. Heat to warm theexhaust storage vessel may come at least partially from a sourceinternal to the vehicle, such as an electric resistance heater or fromthe engine. In some of such embodiments, the engine may or may not beoperating while heat is transferred from the engine to the exhauststorage vessel. Engine coolant may be circulated from the engine to theexhaust storage vessel to transfer heat to the exhaust storage vessel.The exhaust stream may be diverted from the exhaust storage vessel,vented to atmosphere, and heat from the diverted exhaust streamtransferred to the exhaust storage vessel to warm the exhaust storagevessel.

Likewise, in some embodiments of the second method, removing storedcarbon dioxide from the vehicle comprises reducing the pressure and/orincreasing the temperature of the clathrate storage vessel sufficient todissociate the carbon dioxide clathrates stored therein back into carbondioxide and host material and venting gaseous carbon dioxide from theclathrate storage vessel.

The first method may further comprise reusing the dissociated hostmaterial from the exhaust storage vessel to form gas clathrates withadditional at least one gas. Likewise, the second method may furthercomprise reusing the host material in the clathrate storage vessel toform gas clathrates with additional at least one gas.

In some embodiments of the first and the third methods, removing storedcarbon dioxide from the vehicle comprises removing solid carbon dioxideclathrates from the exhaust storage vessel. Likewise, in someembodiments of the second method, removing stored carbon dioxide fromthe vehicle comprises removing solid carbon dioxide clathrates from theclathrate storage vessel.

The first method may further comprise storing gas clathrates for use asfuel. The stored gas clathrates may be separated into at least one gasand a host material. The host material may be reused to form carbondioxide clathrates. The at least one gas may be used as fuel. In thesecond method, the host material may also be reused to form carbondioxide clathrates.

The second method may further comprise tracking which clathratescomprise gas clathrates and which clathrates comprise carbon dioxideclathrates. In some embodiments of the second method, separating storedgas clathrates comprises dissociating primarily only gas clathrateswithout substantially dissociating stored carbon dioxide clathrates.

The first and second methods may further comprise exchanging heat fromthe exhaust stream to stored gas clathrates in order to separate storedgas clathrates into the at least one gas and the host material and toalso cool the exhaust stream. Pressurizing the exhaust stream may occurbefore or after exchanging heat with the stored gas clathrates. When thepressurizing occurs after, the first and second methods may furthercomprise exchanging heat a second time from the exhaust stream to thestored gas clathrates after the exhaust stream has been pressurized, inorder to further cool the exhaust stream.

The methods may further comprise exchanging heat from the exhaust streamto a heat sink external to the vehicle, such as atmospheric air.

In some embodiments of the third method, the fuel comprises gasoline,diesel, compressed natural gas, and/or liquefied natural gas.

The gas clathrates may comprise natural gas clathrates, methaneclathrates, ethane clathrates, propane clathrates, and hydrogenclathrates. Accordingly, the at least one gas may comprise natural gas,methane, ethane, propane, or hydrogen.

The host material may comprise water. The host material may furthercomprise clathrate stabilizers. Examples of clathrate stabilizersinclude but are not limited to carboxylic acids and/orcarboxylate-containing compounds, such as lactic acid, acetic acid, thelactate ion, or the acetate ion; sodium hydroxide and/or a sodium ion;calcium hydroxide and/or a calcium ion; tetrahydrofuran; a surfactant,such as an anionic surfactant, such as alkyl sulfates or alkyl arylsulfonates; an aphron; water soluble salts; clay; oxide particles, suchas magnesium oxide particles; organic compounds, such as phenyl, phenol,alkoxyphenyl, or imidazole-containing compounds.

This disclosure also provides vehicles with reduced emissions. FIG. 1illustrates a vehicle 100 comprising a fuel storage vessel 10 configuredto store gas clathrates. Vehicle 100 also comprises a separation system20 operably connected to the fuel storage vessel and configured todissociate the gas clathrates into a host material and at least one gas.Vehicle 100 further comprises an engine 30 operably connected to theseparation system 20 and configured to utilize the at least one gas asfuel. Vehicle 100 additionally comprises a clathrate formation system 40operably connected to the engine 30 and configured to combine carbondioxide from an exhaust stream from the engine 30 with host material toform carbon dioxide clathrates. Vehicle 100 further comprises an exhauststorage vessel 50 operably connected to the clathrate formation system40 and configured to store carbon dioxide clathrates.

Fuel storage vessel 10 may be configured to receive the at least one gasand the host material and form the gas clathrates within the fuelstorage vessel 10. The fuel storage vessel 10 may be configured toagitate the at least one gas and the host material at a firsttemperature and a first pressure compatible with forming the gasclathrates from the at least one gas and the host material. For example,the fuel storage vessel 10 may comprise a mixing element located withinthe fuel storage vessel 10 that is configured to agitate the at leastone gas and the host material.

The fuel storage vessel 10 and the exhaust storage vessel 50 may eachindependently comprise high-surface-area materials configured forforming clathrates (i.e., gas clathrates in fuel storage vessel 10 andcarbon dioxide clathrates in exhaust storage vessel 50) on the surfaceof the materials. By way of non-limiting example, the high-surface-areamaterial may comprise a graphene-based material, an activated carbon,and/or a metal organic framework, such as a bidentate carboxyliccomprising ligand, a tridentate carboxylic comprising ligand, an azolecomprising ligand, or a squaric acid comprising ligand.

In some embodiments, the fuel storage vessel 10 is configured to bedetachable and reattachable from the remainder of the vehicle 100. Insuch embodiments, the fuel storage vessel 10 may be configured to beexchanged with a different fuel storage vessel 10 that has beenpre-filled with gas clathrates.

The fuel storage vessel 10 may be configured to receive gas clathratesas a solid and/or as a slurry. The fuel storage vessel 10 may beconfigured to maintain gas clathrates as a slurry during storage or as asolid during storage. The solid gas clathrates may be one cohesive solidor may be solid pellets and/or chunks.

The fuel storage vessel 10 and the exhaust storage vessel 50 may eachindependently comprise a refrigeration system configured to maintain aninternal temperature of about 0 degrees Centigrade to about 25 degreesCentigrade. The fuel storage vessel 10 and/or the exhaust storage vessel50 may be configured to maintain an internal temperature of about 0degrees Centigrade to about 20 degrees Centigrade. The fuel storagevessel 10 and/or the exhaust storage vessel 50 may be configured tomaintain an internal temperature of about 0 degrees Centigrade to about15 degrees Centigrade. The fuel storage vessel 10 and/or the exhauststorage vessel 50 may be configured to maintain an internal temperatureof about 0 degrees Centigrade to about 10 degrees Centigrade, includingfrom about 4 degrees Centigrade to about 10 degrees Centigrade.

The refrigeration system for each vessel may independently comprise aheat pipe. The refrigeration system may also comprise a vaporcompression system. The vapor compression system may utilize achlorofluorocarbon, a chlorofluoroolefin, a hydrochlorofluorocarbon, ahydrochloro-fluoroolefin, a hydrofluoroolefin, a hydrochloroolefin, ahydroolefin, a hydrocarbon, a perfluoroolefin, a perfluorocarbon, aperchloroolefin, a perchlorocarbon, and/or a halon. The refrigerationsystem may comprise a vapor absorption system. The vapor absorptionsystem may utilize water, ammonia, and/or lithium bromide. Therefrigeration system may comprise a gas cycle refrigeration system, suchas one that utilizes air. The refrigeration system may comprise astirling cycle refrigeration system. The stirling cycle refrigerationsystem may utilize helium. The stirling cycle refrigeration system maycomprise a free piston stirling cooler. The refrigeration system maycomprise a thermoelectric refrigeration system.

The fuel storage vessel 10 and the exhaust storage vessel 50 may eachindependently comprise insulation. The insulation may comprise at leastone material configured to and compatible with maintaining desiredtemperatures within each vessel. Examples of such materials include, butare not limited to, calcium silicate, cellular glass, elastomeric foam,fiberglass, polyisocyanurate, polystyrene, and polyurethane. Theinsulation may comprise at least one vacuum layer and/or multi-layerinsulation. The insulation may releasably surround at least a portion ofan outer surface of the vessel and/or the insulation may be attached toat least a portion of a surface of the vessel, including an outer and/orinner surface.

The fuel storage vessel 10 and the exhaust storage vessel 50 may each becomprised of structural materials configured to and compatible withmaintaining desired temperatures and pressures within each respectivevessel. The structural material may comprise aluminum, brass, copper,ferretic steel, carbon steel, stainless steel, polytetrafluoroethylene(PTFE), polychlorotrifluoroethylene (PCTFE), vinylidene polyfluoride(PVDF), polyamide (PA), polypropylene (PP), nitrile rubber (NBR),chloroprene (CR), chlorofluorocarbons (FKM), and/or composite materials,including composite materials comprising carbon fibers, glass fibers,and/or aramid fibers.

The fuel storage vessel 10 and the exhaust storage vessel 50 may eachindependently be designed to maintain an internal pressure of about 1bar to about 30 bar, an internal pressure of about 10 bar to about 30bar, an internal pressure of about 10 bar to about 15 bar, an internalpressure of about 15 bar to about 27 bar, or an internal pressure ofabout 20 bar to about 27 bar. Each of the vessels may be designed toleak or vent before burst. Each of the vessels may independently furthercomprise a pressure relief device operably connected to the vessel andconfigured to reduce pressure within the vessel. Examples of a pressurerelief device include, but are not limited to, a pressure relief valveand a rupture disc.

Vehicle 100 may further comprise a pressurizing device operablyconnected to the fuel storage vessel 10 and configured to maintainpressure within the fuel storage vessel 10. Examples of a pressurizingdevice include a moveable press integrated with the vessel, wherein themoveable press is configured to maintain pressure within the vessel. Forexample, the moveable press may include, but is not limited to, ahydraulic press or an electromagnetically activated press. In otherexamples, the pressurizing device may comprise a compressor. Examples ofa compressor include, but are not limited to, a centrifugal compressor,a mixed-flow compressor, an axial-flow compressor, a reciprocatingcompressor, a rotary screw compressor, a rotary vane compressor, ascroll compressor, and a diaphragm compressor.

Vehicle 100 may further comprise a pressurizing device operablyconnected to the exhaust storage vessel 50 and configured to maintainpressure within the exhaust storage vessel 50. Examples of apressurizing device include a moveable press integrated with the vessel,wherein the moveable press is configured to maintain pressure within thevessel. For example, the moveable press may include, but is not limitedto, a hydraulic press or an electromagnetically activated press. Inother examples, the pressurizing device may comprise a compressor.Examples of a compressor include, but are not limited to, a centrifugalcompressor, a mixed-flow compressor, an axial-flow compressor, areciprocating compressor, a rotary screw compressor, a rotary vanecompressor, a scroll compressor, and a diaphragm compressor.

Vehicle 100 may further comprise a pressure monitoring device operablyconnected to the fuel storage vessel 10 and configured to monitor aninternal pressure of the fuel storage vessel 10. Vehicle 100 may furthercomprise a pressure monitoring device operably connected to the exhauststorage vessel 50 and configured to monitor an internal pressure of theexhaust storage vessel 50. In either embodiment, the pressure monitoringdevice may independently comprise a piezoresistive strain gauge, acapacitive sensor, an electromagnetic sensor, a piezoelectric sensor, anoptical sensor, a potentiometric sensor, a thermal conductivity sensor,and/or an ionization sensor.

Vehicle 100 may further comprise a heating system configured and locatedto impart heat energy to the fuel storage vessel 10. The heating systemmay be located internal or external to the vessel. For example, theheating system may be integrated into or attached to a portion of asurface of the fuel storage vessel 10, including external or internalsurfaces. The heating system may be configured to transfer heat energyfrom the coolant used to cool the engine 30. Likewise, the heatingsystem may be configured to transfer heat energy from heat generated bythe engine 30 in any fashion, such as from an exhaust stream generatedby the engine 30. Alternatively or in addition thereto, the heatingsystem may utilize solar energy, ambient temperatures, electricresistance heating elements, microwave heating, electromagnetic heating,and/or dielectric heating to impart heat energy.

Vehicle 100 may further comprise a temperature monitoring systemconfigured to monitor the internal temperature of the fuel storagevessel 10 and/or the exhaust storage vessel 50. The temperaturemonitoring system may comprise a thermostat, a thermistor, athermocouple, and/or a resistive temperature detector.

Vehicle 100 may further comprise an emergency cooling system configuredto rapidly cool the fuel storage vessel 10.

Vehicle 100 may further comprise a control system configured to monitorboth pressure and temperature of the fuel storage vessel and to regulateat least one of pressure and temperature in order to maintain the gasclathrate within a clathrate stability range.

The separation system 20 may comprise a separation vessel operablyconnected to the fuel storage vessel 10. In such embodiments, theseparation system 20 may further comprise a valve operably connectedbetween the separation vessel and the fuel storage vessel 10. The valvemay comprise a passive valve, such as, for example, a ball check valve,a diaphragm check valve, a swing check valve, a stop check valve, or alift check valve. The valve may comprise an active valve, such as, forexample, a globe valve, a butterfly valve, a gate valve, or a ballvalve.

Vehicle 100 may further comprise a transport device operably connectedto the fuel storage vessel 10 and operably connected to the separationvessel and configured to transfer gas clathrates from the fuel storagevessel 10 to the separation vessel. The transport device may beconfigured to transport the gas clathrates as a slurry and/or as asolid, such as solid chunks or pellets.

The transport device may be at least partially located internally withinthe fuel storage vessel 10. Likewise, the transport device may be atleast partially external to the fuel storage vessel 10. Accordingly, thetransport device may be at least partially integrated into a portion ofa surface, including an internal or external surface, of the fuelstorage vessel 10. Additionally, the transport device may be at leastpartially integrated into a portion of a surface, including an internalor external surface, of the separation vessel. Likewise, the transportdevice may be at least partially internal and/or external to theseparation vessel.

The transport device may be configured for moving solid gas clathrate.The transport device may be configured for moving gas clathrate slurry.The transport device may be configured to be hydraulically,mechanically, and/or electrically actuated.

The transport device may comprise an extruder and/or a pump. When thetransport device comprises a pump, the inlet of the pump may be operablyconnected to the fuel storage vessel 10 and an outlet of the pump may beoperably connected to the separation system 20. Examples of the pumpinclude, but are not limited to, a positive displacement pump, a lobepump, an external gear pump, an internal gear pump, a peristaltic pump,a screw pump, a progressive cavity pump, a flexible impeller pump, arotary vane pump, and a centrifugal pump. The pump may be any pumpcompatible with pumping a gas clathrate slurry.

The separation system 20 may be configured to control the rate ofdissociation of the gas clathrates by regulating at least one of thetemperature and the pressure of the gas clathrates within the separationvessel. The separation vessel may be configured to operate at ambienttemperature. The separation vessel may be configured to operate at atemperature that is about the same as an operating temperature of thefuel storage vessel 10. The separation vessel may be configured tooperate at a temperature that is higher than an operating temperature ofthe fuel storage vessel 10.

The separation system 20 may comprise insulation configured to maintainan internal temperature of the separation vessel. The insulation maycomprise at least one material configured to and compatible withmaintaining refrigerated temperatures within the separation vessel.Examples of such materials include, but are not limited to, calciumsilicate, cellular glass, elastomeric foam, fiberglass,polyisocyanurate, polystyrene, and polyurethane. The insulation maycomprise at least one vacuum layer and/or multi-layer insulation. Theinsulation may be attached to at least a portion of a surface of thevessel, including an outer and/or inner surface.

Vehicle 100 may further comprise a refrigeration system configured tomaintain an internal temperature of the separation vessel within a setrange. The set range may be from about 0 degrees Centigrade to about 25degrees Centigrade, including from about 0 degrees Centigrade to about20 degrees Centigrade, including from about 0 degrees Centigrade toabout 15 degrees Centigrade, including from about 0 degrees Centigradeto about 10 degrees Centigrade, and including from about 4 degreesCentigrade to about 10 degrees Centigrade.

The refrigeration system may comprise a heat pipe configured and locatedto control the temperature of the separation vessel. The refrigerationsystem may also comprise a vapor compression system. The vaporcompression system may utilize a chlorofluorocarbon, achlorofluoroolefin, a hydrochlorofluorocarbon, ahydrochloro-fluoroolefin, a hydrofluoroolefin, a hydrochloroolefin, ahydroolefin, a hydrocarbon, a perfluoroolefin, a perfluorocarbon, aperchloroolefin, a perchlorocarbon, and/or a halon. The refrigerationsystem may comprise a vapor absorption system. The vapor absorptionsystem may utilize water, ammonia, and/or lithium bromide. Therefrigeration system may comprise a gas cycle refrigeration system, suchas one that utilizes air. The refrigeration system may comprise astirling cycle refrigeration system. The stirling cycle refrigerationsystem may utilize helium. The stirling cycle refrigeration system maycomprise a free piston stirling cooler. The refrigeration system maycomprise a thermoelectric refrigeration system.

The separation system 20 may comprise a heating system configured andlocated to impart heat energy to the separation vessel. The heatingsystem may be located internal or external to the vessel. For example,the heating system may be integrated into or attached to a portion of asurface of the separation vessel, including external or internalsurfaces. The heating system may be independently configured to transferheat energy from the coolant used to cool the engine 30. Likewise, theheating system may be configured to transfer heat energy from heatgenerated by the engine 30 in any fashion, such as from an exhauststream generated by the engine 30. In some embodiments, the separationsystem 20 and the clathrate formation system 40 may be thermally linked(e.g., by a heat exchanger, a heat pump, or a heat pipe). This thermallink may be configured to transfer heat released during formation ofcarbon dioxide clathrates (thereby helping to cool the clathrateformation system 40) to the separation system 20 to supply heat to aidin dissociating gas clathrates. Alternatively or in addition thereto,the heating system may utilize solar energy, ambient temperatures,electric resistance heating elements, microwave heating, electromagneticheating, and/or dielectric heating to impart heat energy.

The separation system 20 may be configured to maintain a lower pressurein the separation vessel than a pressure maintained in the fuel storagevessel 10. The separation system 20 may be configured to maintain apressure in the separation vessel sufficient to dissociate at least someof the gas clathrates into the at least one gas and the host materialand also maintain a pressure greater than the pressure required fordelivering fuel to the engine 30.

The separation system 20 may be configured to maintain an internalpressure in the separation vessel of about ambient pressure to about 30bar. Separation system 20 may be configured to maintain an internalpressure in the separation vessel of about 5 bar to about 20 bar.Separation system 20 may be configured to maintain an internal pressurein the separation vessel of about 10 bar to about 15 bar. Separationsystem 20 may be configured to maintain an internal pressure in theseparation vessel of about ambient pressure to about 10 bar. Separationsystem 20 may be configured to maintain an internal pressure in theseparation vessel of about ambient pressure. The separation vessel maybe designed to leak or vent before burst.

The separation system 20 may further comprise a pressure reducing valveoperably connected to the fuel storage vessel 10 and the separationvessel, wherein the pressure reducing valve is configured to reduce thepressure of gas clathrates transferred from the fuel storage vessel 10to the separation vessel.

Separation system 20 may be configured to receive a continuous supply ofgas clathrates while vehicle 100 is operating. Alternatively, separationsystem 20 may be configured to periodically receive a batch of gasclathrates while vehicle 100 is operating. Furthermore, separationsystem 20 may be configured to receive a variable supply of gasclathrates based on fuel requirements of the engine 30. Likewise, theseparation system 20 may be configured to control the rate ofdissociation of the gas clathrates based on fuel requirements of the 30,such as by regulating at least one of the temperature and the pressureof the gas clathrates within the separation vessel.

The separation vessel may comprise a chamber configured to dissociatethe gas clathrates into at least one gas and host material.Alternatively or in addition thereto, the separation vessel may comprisea conduit configured to continuously dissociate the gas clathrates intoat least one gas and host material.

The separation vessel comprises a host material outlet configured forremoving the host material from the separation vessel.

The separation system 20 may further comprise a temperature monitoringsystem configured to monitor the internal temperature of the separationvessel. The temperature monitoring system may comprise a thermostat, athermistor, a thermocouple, and/or a resistive temperature detector.

Vehicle 100 may further comprise an emergency cooling system configuredto rapidly cool the separation vessel.

The separation system 20 may further comprise a pressure monitoringdevice operably connected to the separation vessel and configured tomonitor an internal pressure of the separation vessel. The pressuremonitoring device may independently comprise a piezoresistive straingauge, a capacitive sensor, an electromagnetic sensor, a piezoelectricsensor, an optical sensor, a potentiometric sensor, a thermalconductivity sensor, and/or an ionization sensor.

The separation system 20 may further comprise a pressure relief deviceoperably connected to the separation vessel and configured to reducepressure within the separation vessel. Examples of a pressure reliefdevice include, but are not limited to, a pressure relief valve and arupture disc.

The separation system 20 may further comprise a pressurizing deviceoperably connected to the separation vessel and configured to maintainpressure within the separation vessel. Examples of a pressurizing deviceinclude a moveable press integrated with the vessel, wherein themoveable press is configured to maintain pressure within the vessel. Forexample, the moveable press may include, but is not limited to, ahydraulic press or an electromagnetically activated press. In otherexamples, the pressurizing device may comprise a compressor. Examples ofa compressor include, but are not limited to, a centrifugal compressor,a mixed-flow compressor, an axial-flow compressor, a reciprocatingcompressor, a rotary screw compressor, a rotary vane compressor, ascroll compressor, and a diaphragm compressor.

The separation vessel may comprise a gas outlet configured for removingdissociated at least one gas from the separation vessel. The separationsystem 20 may further comprise a control valve operably connected to thegas outlet and to the engine 30, wherein the control valve is configuredto control release of stored at least one gas from the separationvessel. The separation system 20 may further comprise a metering systemconfigured to control introduction of stored at least one gas to theengine 30. The metering system may comprise a gas flow meter configuredto measure the flow rate of the stored at least one gas released fromthe separation vessel. The separation system 20 may further comprise atransport device configured to transport the dissociated at least onegas from the separation vessel to the engine 30, wherein the transportdevice is operably connected to the separation vessel and to the engine30. The transport device may be configured to control the transport ofthe dissociated at least one gas based on fuel requirements of theengine 30. The transport device may comprise a compressor. Examples of acompressor include, but are not limited to, a centrifugal compressor, amixed-flow compressor, an axial-flow compressor, a reciprocatingcompressor, a rotary screw compressor, a rotary vane compressor, ascroll compressor, and a diaphragm compressor.

Vehicle 100 may further comprise a gas storage vessel configured tostore the dissociated at least one gas removed from the separationsystem 20, wherein the gas storage vessel is operably connected to theseparation system 20 and is operably connected to the engine 30. In suchembodiments, the vehicle 100 may further comprise a control valveoperably connected to the gas storage vessel and to the engine 30,wherein the control valve is configured to control release of stored atleast one gas from the gas storage vessel. Vehicle 100 may furthercomprise a metering system configured to control introduction of storedat least one gas to the engine 30. The metering system may comprise agas flow meter configured to measure the flow rate of the stored atleast one gas released from the gas storage vessel. Vehicle 100 mayfurther comprise a transport device configured to transport thedissociated at least one gas from the gas storage vessel to the engine30, wherein the transport device is operably connected to the gasstorage vessel and to the engine 30. The transport device may beconfigured to control the transport of the dissociated at least one gasbased on fuel requirements of the engine 30. The transport device maycomprise a compressor. Examples of a compressor include, but are notlimited to, a centrifugal compressor, a mixed-flow compressor, anaxial-flow compressor, a reciprocating compressor, a rotary screwcompressor, a rotary vane compressor, a scroll compressor, and adiaphragm compressor.

Vehicle 100 may further comprise a control valve operably connected tothe separation system 20 and to the gas storage vessel, wherein thecontrol valve is configured to control release of stored at least onegas from the separation vessel. Vehicle 100 may further comprise ametering system configured to control introduction of stored at leastone gas from the separation system to the gas storage vessel. Themetering system may comprise a gas flow meter configured to measure theflow rate of the stored at least one gas released from the separationvessel. Vehicle 100 may further comprise a transport device configuredto transport the dissociated at least one gas from the separation vesselto the gas storage vessel, wherein the transport device is operablyconnected to the separation vessel and to the gas storage vessel. Thetransport device may be configured to control the transport of thedissociated at least one gas based on fuel requirements of the engine30. The transport device may comprise a compressor. Examples of acompressor include, but are not limited to, a centrifugal compressor, amixed-flow compressor, an axial-flow compressor, a reciprocatingcompressor, a rotary screw compressor, a rotary vane compressor, ascroll compressor, and a diaphragm compressor.

In some embodiments, the separation system 20 is integrated with thefuel storage vessel 10 and the separation system 20 is configured tocontrol the rate of dissociation of the gas clathrates by regulating atleast one of the temperature and the pressure of the gas clathrateswithin the fuel storage vessel 10. For example, the temperature and thepressure may be varied to a second temperature and a second pressureduring dissociation of the gas clathrates. The second temperature may beabout 0 degrees Centigrade to about 25 degrees Centigrade, about 0degrees Centigrade to about 20 degrees Centigrade, about 0 degreesCentigrade to about 15 degrees Centigrade, about 0 degrees Centigrade toabout 10 degrees Centigrade, or about 4 degrees Centigrade to about 10degrees Centigrade. The second pressure may be about ambient pressure toabout 30 bar, about 5 bar to about 20 bar, about 10 bar to about 15 bar,or about ambient pressure to about 10 bar.

In such embodiments, the fuel storage vessel 10 may comprise a gasoutlet configured and located for removing gas from the fuel storagevessel 10. The gas may comprise dissociated at least one gas locatedwithin the fuel storage vessel 10.

The separation system 20 may further comprise a heat pipe configured andlocated to modulate the temperature of the fuel storage vessel 10. Theseparation system 20 may further comprise a heating system configuredand located to impart heat energy to the fuel storage vessel 10. Theheating system may be configured to transfer heat energy from thecoolant used to cool the engine 30. Likewise, the heating system may beconfigured to transfer heat energy from heat generated by the engine 30in any fashion, such as from an exhaust stream generated by the engine30. Alternatively or in addition thereto, the heating system may utilizesolar energy, ambient temperatures, electric resistance heatingelements, microwave heating, electromagnetic heating, and/or dielectricheating to impart heat energy. The heating system may be locatedinternal or external to the fuel storage vessel 10. For example, theheating system may be integrated into or attached to a portion of asurface of the fuel storage vessel 10, including external or internalsurfaces.

The separation system 20 may be configured to reduce the pressure in thefuel storage vessel 10 sufficient to dissociate at least some of the gasclathrates into the at least one gas and the host material, but stillmaintain a pressure greater than the pressure required for deliveringdissociated gas to the engine 30.

The vehicle 100 may comprise a cooling device configured to reduce thetemperature of the dissociated at least one gas prior to introduction ofthe dissociated at least one gas to the engine 30. The cooling devicemay comprise a heat exchanger. The heat exchanger may be configured tobe cooled by ambient air. The heat exchanger may be configured to becooled by a coolant also used to cool the engine 30. The heat exchangermay be configured to be cooled by the fuel storage vessel 10. The heatexchanger may be configured to be cooled by the separation system 20.The cooling device may comprise a refrigerated coil configured to coolthe at least one gas.

The vehicle 100 may comprise a transport device configured to transportthe dissociated at least one gas from the separation system 20 to theengine 30, wherein the transport device is operably connected to theseparation system 20 and to the engine 30. The transport device may beconfigured to control the transport of the dissociated at least one gasbased on fuel requirements of the engine 30. The transport device maycomprise a compressor. Examples of a compressor include, but are notlimited to, a centrifugal compressor, a mixed-flow compressor, anaxial-flow compressor, a reciprocating compressor, a rotary screwcompressor, a rotary vane compressor, a scroll compressor, and adiaphragm compressor. In such embodiments, the vehicle 100 may furthercomprise a cooling device, such as the cooling device disclosed above,configured to reduce the temperature of the dissociated at least one gasprior to introduction of the dissociated at least one gas to the engine30.

The vehicle 100 may comprise a moisture-removal system configured toremove water from the dissociated at least one gas prior to introductionof the dissociated at least one gas to the engine 30. Themoisture-removal system may comprise, by way of non-limiting example, adehumidifier, a dryer, or a molecular sieve column. In some embodiments,the moisture-removal system is part of the separation system 20.

The vehicle 100 may comprise a host material storage vessel configuredto supply host material to the clathrate formation system 40, whereinthe host material storage vessel is operably connected to the clathrateformation system 40. The vehicle 100 may comprise a transport deviceconfigured to transport host material from the host material storagevessel to the clathrate formation system 40. The transport device mayfurther be configured to transport host material from the separationsystem 20 to the host material storage vessel. The host material storagevessel may be configured to store previously unused host material.

The vehicle 100 may comprise a filter configured to separate non-carbonproducts from the exhaust stream.

The vehicle 100 may comprise a catalytic converter configured to convertcarbon monoxide and uncombusted hydrocarbons to carbon dioxide.

The clathrate formation system 40 may be configured to utilizecombustion produced water as at least a portion of the host material inthe formation of carbon dioxide clathrates. In addition to carbondioxide clathrates, the clathrate formation system 40 may be configuredto also form carbon monoxide clathrates and partially combustedhydrocarbon clathrates. For example, the clathrate formation system 40may be configured to control the pressure and temperature of the exhauststream and the host material sufficient to form partially combustedhydrocarbon clathrates with partially combusted hydrocarbons and hostmaterial, to form carbon monoxide clathrates with carbon monoxide andhost material, and/or to form carbon dioxide clathrates with carbondioxide and host material. Likewise, the exhaust storage vessel 50 mayalso be configured to store carbon monoxide clathrates and partiallycombusted hydrocarbon clathrates in addition to carbon dioxideclathrates.

The clathrate formation system 40 may comprise a cooling systemconfigured to cool the exhaust stream. The cooling system may beoperably connected with the separation system 20 and may be configuredto transfer heat from the exhaust stream to the separation system 20.The cooling system may comprise a heat exchanger configured to transferheat from the exhaust stream to an external heat sink, such as ambientair.

The clathrate formation system 40 may comprise a pressurization system.The pressurization system may comprise a compressor. Examples of acompressor include, but are not limited to, a centrifugal compressor, amixed-flow compressor, an axial-flow compressor, a reciprocatingcompressor, a rotary screw compressor, a rotary vane compressor, ascroll compressor, and a diaphragm compressor.

The clathrate formation system 40 may comprise a formation vesseloperably connected to the exhaust storage vessel 50.

The clathrate formation system 40 may further comprise a carbon dioxideremoval system configured to separate carbon dioxide from the exhauststream and deliver the removed carbon dioxide to the formation vessel.The carbon dioxide removal system may comprise a removal vessel operablyconnected to the exhaust stream and the formation vessel.

The removal vessel may be configured to contact the exhaust stream withat least one separation fluid. The separation fluid may comprise achemical solvent. The separation fluid may comprise a physical solvent.Examples of the separation fluid include fluids comprising analkanolamine, a monoethanolamine, a diethanolamine, amethyldiethanolamine, a triethanolamine, and/or piperazine. Theseparation fluid may be a liquid. The separation fluid may comprise hostmaterial.

The vehicle 100 may further comprise a regeneration system configured toseparate carbon dioxide from the separation fluid and operably coupledto the removal vessel. The regeneration system may comprise aregeneration vessel operably coupled to the removal vessel andconfigured to heat the separation fluid. The regeneration vessel may beconfigured to operate on a batch basis. The regeneration vessel may beconfigured to operate on a continuous basis. The regeneration vessel maycomprise a tank. The regeneration vessel may comprise a conduit.

In some embodiments, the removal vessel is configured to contact theexhaust stream with an alkali carbonate, such as sodium carbonate and/orpotassium carbonate. In such embodiments, the vehicle 100 may furthercomprise a regeneration system configured to separate carbon dioxidefrom the alkali carbonate and operably coupled to the removal vessel.The regeneration system may comprise a regeneration vessel operablycoupled to the removal vessel and configured to heat the alkalicarbonate. The regeneration vessel may be configured to operate on abatch basis or on a continuous basis. The regeneration vessel maycomprise a tank and/or a conduit.

In some embodiments, the removal vessel comprises a membrane configuredto separate carbon dioxide from the exhaust stream. The membrane maycomprise a polymer, such as a cellulose acetate polymer, a polyimidepolymer, a polyamide polymer, a polycarbonate polymer, a polysulfonepolymer, and/or a polyetherimide polymer. The membrane may comprise flatsheets. The flat sheets may be spiral-wound. The membrane may comprisehollow fibers.

The removal vessel may be configured to operate on a batch basis. Forexample, the removal vessel may comprise a tank. The removal vessel maybe configured to operate on a continuous basis. For example, the removalvessel may comprise a conduit.

The clathrate formation system 40 may be configured to control the rateof formation of the carbon dioxide clathrates by regulating at least oneof the temperature and the pressure of exhaust gases within theformation vessel. The formation vessel may be configured to operate at atemperature and/or a pressure that is about the same as an operatingtemperature of the fuel storage vessel 10.

The formation vessel may further comprise insulation configured tomaintain an internal temperature of the formation vessel. The insulationmay comprise at least one material configured to and compatible withmaintaining desired temperatures within the formation vessel. Examplesof such materials include, but are not limited to, calcium silicate,cellular glass, elastomeric foam, fiberglass, polyisocyanurate,polystyrene, and polyurethane. The insulation may comprise at least onevacuum layer and/or multi-layer insulation. The insulation mayreleasably surround at least a portion of an outer surface of the vesseland/or the insulation may be attached to at least a portion of a surfaceof the vessel, including an outer and/or inner surface.

The vehicle 100 may further comprise a refrigeration system configuredto maintain an internal temperature of the formation vessel within a setrange. The refrigeration system may also be configured to cool theexhaust stream. The refrigeration system may be integrated with arefrigeration system of the fuel storage vessel 10, if present. The setrange may be from about 0 degrees Centigrade to about 25 degreesCentigrade, including from about 0 degrees Centigrade to about 20degrees Centigrade, including from about 0 degrees Centigrade to about15 degrees Centigrade, including from about 0 degrees Centigrade toabout 10 degrees Centigrade, and including from about 4 degreesCentigrade to about 10 degrees Centigrade.

The refrigeration system may comprise a heat pipe configured and locatedto control the temperature of the formation vessel. The heat pipe may beoperably connected to the separation system. The refrigeration systemmay also comprise a vapor compression system. The vapor compressionsystem may utilize a chlorofluorocarbon, a chlorofluoroolefin, ahydrochlorofluorocarbon, a hydrochloro-fluoroolefin, ahydrofluoroolefin, a hydrochloroolefin, a hydroolefin, a hydrocarbon, aperfluoroolefin, a perfluorocarbon, a perchloroolefin, aperchlorocarbon, and/or a halon. The refrigeration system may comprise avapor absorption system. The vapor absorption system may utilize water,ammonia, and/or lithium bromide. The refrigeration system may comprise agas cycle refrigeration system, such as one that utilizes air. Therefrigeration system may comprise a stirling cycle refrigeration system.The stirling cycle refrigeration system may utilize helium. The stirlingcycle refrigeration system may comprise a free piston stirling cooler.The refrigeration system may comprise a thermoelectric refrigerationsystem.

The clathrate formation system 40 may be configured to generate aninternal pressure in the formation vessel of about ambient pressure toabout 30 bar, an internal pressure of about 10 bar to about 30 bar, aninternal pressure of about 10 bar to about 15 bar, an internal pressureof about 15 bar to about 27 bar, or an internal pressure of about 20 barto about 27 bar. The formation vessel may be designed to leak or ventbefore burst. Each of the vessels may independently further comprise apressure relief device operably connected to the vessel and configuredto reduce pressure within the vessel. Examples of a pressure reliefdevice include, but are not limited to, a pressure relief valve and arupture disc.

The clathrate formation system 40 may be configured to pressurize theexhaust stream in the formation vessel without substantially increasingback pressure on the exhaust ports of the engine 30. In suchembodiments, the clathrate formation system 40 may comprise a valveoperably connected to the formation vessel, wherein the valve isconfigured to control introduction of the exhaust stream to theformation vessel. The clathrate formation system 40 may be configured tosequentially introduce batches of the exhaust stream to the formationvessel. For example, introduction of the exhaust stream batches to theformation vessel may be timed to coincide with the closing of exhaustports of the engine 30.

The clathrate formation system 40 may further comprise at least oneholding vessel for temporarily storing the exhaust stream at a lowpressure prior to introduction of the exhaust stream to the formationvessel for pressurizing. The low pressure may be less than the pressureat which carbon dioxide clathrates are formed in the formation vessel.The low pressure may be substantially equal to what the pressure of theexhaust stream at an exhaust port of the engine 30 would be if theclathrate formation system 40 and the exhaust storage vessel 50 were notconnected to the engine 30. The low pressure may be about equal toatmospheric pressure.

The clathrate formation system 40 may comprise a compressor, wherein aninlet of the compressor is operably connected to exhaust ports of theengine 30 and an outlet of the compressor is operably connected to theformation vessel. The compressor may be configured to reduce backpressure on exhaust ports of the engine 30 to be substantially equal towhat the pressure at the exhaust ports would be if the clathrateformation system 40 and exhaust storage vessel 50 were not connected tothe exhaust stream. The compressor may be configured to minimize backpressure on the exhaust ports of the engine 30 while pressurizing theformation vessel. Examples of a compressor include, but are not limitedto, a centrifugal compressor, a mixed-flow compressor, an axial-flowcompressor, a reciprocating compressor, a rotary screw compressor, arotary vane compressor, a scroll compressor, and a diaphragm compressor.

The formation vessel may comprise a chamber configured to form batchesof carbon dioxide clathrates and/or the formation vessel may comprise aconduit operably connected to the exhaust storage vessel 50 andconfigured to continuously form carbon dioxide clathrates.

The clathrate formation system 40 may comprise a moveable pressintegrated with the formation vessel and configured to pressurize theformation vessel. For example, the moveable press may include, but isnot limited to, a hydraulic press or an electromagnetically activatedpress.

The clathrate formation system 40 may further comprise a temperaturemonitoring system configured to monitor the internal temperature of theformation vessel. The temperature monitoring system may comprise athermostat, a thermistor, a thermocouple, and/or a resistive temperaturedetector.

The clathrate formation system 40 may further comprise a pressuremonitoring device operably connected to the formation vessel andconfigured to monitor an internal pressure of the formation vessel. Forexample, the pressure monitoring device may comprise a piezoresistivestrain gauge, a capacitive sensor, an electromagnetic sensor, apiezoelectric sensor, an optical sensor, a potentiometric sensor, athermal conductivity sensor, and/or an ionization sensor.

The clathrate formation system 40 may further comprise a pressure reliefdevice operably connected to the formation vessel and configured toreduce pressure within the formation vessel. Examples of a pressurerelief device include, but are not limited to, a pressure relief valveand a rupture disc.

The vehicle 100 may further comprise a transport device operablyconnected to the formation vessel and the exhaust storage vessel 50 andconfigured to transfer carbon dioxide clathrates from the formationvessel to the exhaust storage vessel 50. The transport device may beconfigured to transport the carbon dioxide clathrates as a slurry and/oras a solid, such as solid chunks or pellets.

The transport device may be at least partially located internally withinthe formation vessel. Likewise, the transport device may be at leastpartially external to the formation vessel. Accordingly, the transportdevice may be at least partially integrated into a portion of a surface,including an internal or external surface, of the formation vessel.Additionally, the transport device may be at least partially integratedinto a portion of a surface, including an internal or external surface,of the exhaust storage vessel 50. Likewise, the transport device may beat least partially internal and/or external to the exhaust storagevessel 50.

The transport device may be configured for moving solid carbon dioxideclathrate. The transport device may be configured for moving solidcarbon dioxide slurry. The transport device may be configured to behydraulically, mechanically, and/or electrically actuated.

The transport device may comprise an extruder and/or a pump. When thetransport device comprises a pump, the inlet of the pump may be operablyconnected to the formation vessel and an outlet of the pump may beoperably connected to the exhaust storage vessel 50. Examples of thepump include, but are not limited to, a positive displacement pump, alobe pump, an external gear pump, an internal gear pump, a peristalticpump, a screw pump, a progressive cavity pump, a flexible impeller pump,a rotary vane pump, and a centrifugal pump. The pump may be any pumpcompatible with pumping a carbon dioxide clathrate slurry.

The clathrate formation system 40 may be integrated with the exhauststorage vessel 50. The clathrate formation system 40 may be configuredto form carbon dioxide clathrates by regulating at least one of thetemperature and the pressure of carbon dioxide and host material withinthe exhaust storage vessel 50 to be compatible with forming carbondioxide clathrates. For example, the temperature may be regulated to beabout 0 degrees Centigrade to about 25 degrees Centigrade, may beregulated to be about 0 degrees Centigrade to about 20 degreesCentigrade, may be regulated to be about 0 degrees Centigrade to about15 degrees Centigrade, may be regulated to be about 0 degrees Centigradeto about 10 degrees Centigrade, or may be regulated to be about 4degrees Centigrade to about 10 degrees Centigrade. In another example,the pressure may be regulated to be about 1 bar to about 30 bar, thepressure may be regulated to be about 10 bar to about 30 bar, thepressure may be regulated to be about 10 bar to about 15 bar, thepressure may be regulated to be about 15 bar to about 27 bar, or thepressure may be regulated to be about 20 bar to about 27 bar.

Likewise, the exhaust storage vessel 50 may be configured to agitate thecarbon dioxide and the host material at a temperature and a pressurecompatible with forming the carbon dioxide clathrates. For example, theexhaust storage vessel 50 may comprise a mixing element located withinthe exhaust storage vessel 50 and configured to agitate the carbondioxide and the host material.

The clathrate formation system 40 may further comprise a heat pipeconfigured and located to modulate the temperature of the exhauststorage vessel 50.

The clathrate formation system 40 may be configured to receive acontinuous supply of carbon dioxide or may be configured to periodicallyreceive a batch of carbon dioxide, while the vehicle 100 is operating.The clathrate formation system 40 may be configured to receive avariable supply of the exhaust stream based on the quantity of exhaustproduced by the engine 30.

The exhaust storage vessel 50 may be configured to receive the carbondioxide clathrates as a solid and/or as a slurry.

The exhaust storage vessel 50 may be configured for removal of storedcarbon dioxide from the vehicle 100 when the vehicle 100 is otherwisenot in use. The exhaust storage vessel 50 may be configured to reducethe pressure and/or increase the temperature of the exhaust storagevessel 50 sufficient to dissociate the stored carbon dioxide clathratesinto carbon dioxide and host material. For example, the exhaust storagevessel 50 may be configured to sufficiently warm stored carbon dioxideclathrates so as to liquefy the host material and gasify the carbondioxide. The exhaust storage vessel 50 may comprise an outlet configuredfor removal of dissociated carbon dioxide. The exhaust storage vessel 50may also comprise an outlet configured for removal of dissociated hostmaterial.

Vehicle 100 may further comprise a heating system configured and locatedto impart heat energy to the exhaust storage vessel 50. The heatingsystem may be located internal or external to the vessel. For example,the heating system may be integrated into or attached to a portion of asurface of the exhaust storage vessel 50, including external or internalsurfaces. The heating system may be independently configured to transferheat energy from the coolant used to cool the engine 30. Likewise, theheating system may be configured to transfer heat energy from heatgenerated by the engine 30 in any fashion, such as from an exhauststream generated by the engine 30. For example, the heating system maybe configured to divert the exhaust stream from the clathrate formationsystem 40 and also configured to transfer heat from the diverted exhauststream to the exhaust storage vessel 50. In that example, the heatingsystem may be further configured to divert the exhaust stream from theexhaust storage vessel 50 and vent the exhaust stream to atmosphere.Alternatively or in addition thereto, the heating system may utilizesolar energy, ambient temperatures, electric resistance heatingelements, microwave heating, electromagnetic heating, and/or dielectricheating to impart heat energy.

The vehicle 100 may further comprise a recycle system configured totransfer dissociated host material from the exhaust storage vessel 50 tothe fuel storage vessel 10. The recycle system may comprise a filterconfigured to clean dissociated host material prior to transfer of thedissociated host material to the fuel storage vessel 10. The recyclesystem may comprise a transfer device configured to transfer thedissociated host material to the fuel storage vessel 10.

The exhaust storage vessel 50 may be configured for removal of solidand/or slurry carbon dioxide clathrates from the exhaust storage vessel50.

The exhaust storage vessel 50 may be configured to maintain carbondioxide clathrates as a solid and/or slurry until removal of carbondioxide from the vehicle 100 is intended.

The exhaust storage vessel 50 may be configured to be detachable andreattachable from the remainder of the vehicle 100. For example, theexhaust storage vessel 50 may be configured to be exchanged with adifferent exhaust storage vessel 50 that has been emptied of carbondioxide clathrates.

The vehicle 100 may further comprise a sensor configured to monitor theamount of carbon dioxide clathrates in the exhaust storage vessel 50.The sensor may be configured to measure a mass of the carbon dioxideclathrates. The sensor may be configured to measure a vapor pressure ofcarbon dioxide gas present in the exhaust storage vessel 50. The sensormay be configured to determine a concentration of carbon dioxide presentin the exhaust storage vessel 50. The sensor may be configured tomonitor the amount of carbon dioxide removed from the exhaust storagevessel 50.

The vehicle 100 may alternatively comprise a dissociation vesseloperably connected to the exhaust storage vessel 50 and configured toreceive carbon dioxide clathrates from the exhaust storage vessel 50.The dissociation vessel may be configured for removal of stored carbondioxide from the vehicle 100 when the vehicle 100 is otherwise not inuse. The dissociation vessel may be configured to reduce the pressureand/or increase the temperature of the dissociation vessel sufficient todissociate the stored carbon dioxide clathrates into carbon dioxide andhost material.

The vehicle 100 may further comprise a temperature monitoring systemconfigured to monitor the internal temperature of the exhaust storagevessel 50. The temperature monitoring system may comprise a thermostat,a thermistor, a thermocouple, and/or a resistive temperature detector.

The vehicle 100 may further comprise a control system configured tomonitor both pressure and temperature of the exhaust storage vessel 50and configured to regulate at least one of pressure and temperature inorder to maintain the carbon dioxide clathrate within a clathratestability range.

The vehicle 100 may further comprise a recycle system configured totransfer dissociated host material from the separation system 20 to theclathrate formation system 40. The recycle system may further comprise ahost material storage vessel configured to store dissociated hostmaterial from the separation system 20. The recycle system may comprisea transfer device configured to transfer the dissociated host materialto the clathrate formation system 40. The recycle system may comprise afilter configured to clean dissociated host material prior to transferof the dissociated host material to the clathrate formation system 40;e.g., to remove a clathrate stabilizer more suitable for gas clathratesthan for carbon dioxide clathrates. The recycle system may comprise asupply reservoir configured to add a component to the host materialprior to transfer of the dissociated host material to the clathrateformation system 40; e.g., to add a clathrate stabilizer more suitablefor carbon dioxide clathrates than for gas clathrates.

FIG. 2 illustrates an additional embodiment of a vehicle with reducedemissions. FIG. 2 illustrates a vehicle 200 comprising a clathratestorage vessel 110 configured to store gas clathrates and carbon dioxideclathrates. The gas clathrates and the carbon dioxide clathrates may bestored within a common compartment or within separate compartmentswithin the clathrate storage vessel 110. For example, separatecompartments may have fixed, predefined volumes and locations, or may bevariably partitioned, e.g., by a flexible bladder or by a slidablepartition. The functions of the fuel storage vessel 10 and the exhauststorage vessel 50 of the vehicle 100 may be performed by the clathratestorage vessel 110 of the vehicle 200. Accordingly, the disclosureregarding the fuel storage vessel 10 and the disclosure regarding theexhaust storage vessel 50 may be applicable to the clathrate storagevessel 110 and vice versa. Likewise, the disclosure regarding theseparation system 20 and the clathrate formation system 40 may apply tothe separation system 120 and the clathrate formation system 140 of thevehicle 200 and vice versa.

The separation system 120 may be configured to dissociate the gasclathrates into a host material and at least one gas. The vehicle 200may further comprise an engine 130 configured to utilize the at leastone gas as fuel. The clathrate formation system 140 may be configured tocombine carbon dioxide from an exhaust stream from the engine 130 withhost material to form carbon dioxide clathrates.

The vehicle 200 may further comprise a control system configured to feedprimarily stored gas clathrates to the separation system 120 withoutfeeding stored carbon dioxide clathrates to the separation system 120.

The vehicle 200 may further comprise a tracking system configured tomonitor which clathrates comprise gas clathrates and which clathratescomprise carbon dioxide clathrates. The tracking system may comprise anoptical tracking system, a mechanical tracking system, a magneticsensor, and/or a hall effect sensor.

The clathrate storage vessel 110 may be configured to receive the atleast one gas and the host material and configured to form the gasclathrates within the clathrate storage vessel 110, similar as disclosedabove for the fuel storage vessel 10. The clathrate storage vessel 110may comprise high-surface-area materials configured for formingclathrates on the surface of the materials. The high-surface-areamaterials may be configured for forming gas clathrates and carbondioxide clathrates, where formation depends upon the conditions withinthe clathrate storage vessel 110 and the gases present. Thehigh-surface-area materials may be the same as disclosed above for thefuel storage vessel 10. The high-surface-area materials may comprisepart of a moveable surface operably connected to the separation system120, such as a conveyor belt, rotatable drum or disk, and/or moveablestring.

The clathrate storage vessel 110 may be configured to be detachable andreattachable from the remainder of the vehicle 200. For example, theclathrate storage vessel 110 may be configured to be exchanged with adifferent clathrate storage vessel 110 that has had carbon dioxideclathrates removed and been pre-filled with gas clathrates.

The clathrate storage vessel 110 may be configured to receive the gasclathrates as a slurry or a solid. The clathrate storage vessel 110 maybe configured to maintain the gas clathrates as a slurry or a solid,such as solid pellets or chunks.

The clathrate storage vessel 110 may comprise insulation. The disclosureregarding insulation options for the fuel storage vessel 10 also applyto the insulation options for the clathrate storage vessel 110.Likewise, the clathrate storage vessel 110 may comprise a refrigerationsystem configured to maintain an internal temperature of the clathratestorage vessel 110 within a set range. The disclosure regardingrefrigeration system options and set range options for the fuel storagevessel 10 also applies to refrigeration system options and set rangeoptions for the clathrate storage vessel 110. Similarly, the structuralmaterial options disclosed for the fuel storage vessel 10 also apply tothe structural material options for the clathrate storage vessel 110.

The vehicle 200 may further comprise a sensor configured to monitor theamount of gas clathrates and/or carbon dioxide clathrates in theclathrate storage vessel 110. The disclosure regarding sensor optionsfor vehicle 100 also applies to the sensor options for vehicle 200.

The clathrate storage vessel 110 may be designed to maintain an internalpressure of about 1 bar to about 30 bar, including the narrower rangesdisclosed for the fuel storage vessel 10. The disclosure regardingoptions for the fuel storage vessel 10 also apply to the options for theclathrate storage vessel 110. For example, the clathrate storage vessel110 may be designed to leak or vent before burst. In other examples, theclathrate storage vessel 110 may be operably connected to a pressuremonitoring device, a pressurizing device, and/or a pressure reliefdevice. The disclosure regarding pressure monitoring device,pressurizing device, and/or pressure relief device options for thevehicle 100 also applies to pressure monitoring device, pressurizingdevice, and/or pressure relief device options for the vehicle 200.

The vehicle 200 may further comprise a heating system configured andlocated to impart heat energy to the clathrate storage vessel 110. Thevehicle 200 may further comprise a temperature monitoring systemconfigured to monitor the internal temperature of the clathrate storagevessel 110. The vehicle 200 may further comprise an emergency coolingsystem configured to rapidly cool the clathrate storage vessel 110. Thevehicle 200 may further comprise a control system configured to monitorboth pressure and temperature and to regulate at least one of thepressure and temperature in order to maintain clathrate within aclathrate stability range. The disclosure regarding a heating system, atemperature monitoring system, an emergency cooling system, and acontrol system for the vehicle 100 and the fuel storage vessel 10 alsoapplies to the same for the vehicle 200 and the clathrate storage vessel110.

In some embodiments of the vehicle 200, the separation system 120comprises a separation vessel operably connected to the clathratestorage vessel 110. The separation system 120 may further comprise avalve operably connected between the separation vessel 120 and theclathrate storage vessel 110. The valve may comprise a passive valve,such as, for example, a ball check valve, a diaphragm check valve, aswing check valve, a stop check valve, or a lift check valve. The valvemay comprise an active valve, such as, for example, a globe valve, abutterfly valve, a gate valve, or a ball valve.

The vehicle 200 may further comprise a transport device operablyconnected to the clathrate storage vessel 110 and operably connected tothe separation vessel and configured to transfer gas clathrates from theclathrate storage vessel 110 to the separation vessel. The transportdevice may comprise a moveable surface, such as a conveyor belt, arotating drum, a string, and/or a rotating disk. The moveable surfacemay comprise a high-surface-area material, such as the high-surface-areamaterials disclosed above for the fuel storage vessel 10. The disclosureregarding options for a transport device operably connected to the fuelstorage vessel 10 and the separation vessel of vehicle 100 also appliesto options for a transport device operably connected to the clathratestorage vessel 110 and the separation vessel of the vehicle 200.

The separation system 120 may be configured to control the rate ofdissociation of the gas clathrates by regulating at least one of thetemperature and the pressure of the gas clathrates within the separationvessel. The separation vessel may be configured to operate at ambienttemperature. The separation vessel may be configured to operate at atemperature that is about the same as an operating temperature of theclathrate storage vessel 110. The separation vessel may be configured tooperate at a temperature that is higher than an operating temperature ofthe clathrate storage vessel 110.

The separation system 120 may further comprise insulation configured tomaintain an internal temperature of the separation vessel. The vehicle200 may further comprise a refrigeration system configured to maintainan internal temperature of the separation vessel within a set range. Therefrigeration system may be integrated with the refrigeration system ofthe clathrate storage vessel 110. The disclosure regarding options forinsulation and a refrigeration system, including the set range, for theseparation vessel of vehicle 100 also applies to options for insulationand a refrigeration system for the separation vessel of the vehicle 200.

The separation system 120 may further comprise a heat pipe configuredand located to control the temperature of the separation vessel. Theseparation system 120 may further comprise a heating system configuredand located to impart heat energy to the separation vessel. In someembodiments, the separation system 120 and the clathrate formationsystem 140 may be thermally linked (e.g., by a heat exchanger, a heatpump, or a heat pipe). This thermal link may be configured to transferheat released during formation of carbon dioxide clathrates (therebyhelping to cool the clathrate formation system 140) to the separationsystem 120 to supply heat to aid in dissociating gas clathrates. Thedisclosure regarding options for a heating system of the separationvessel of vehicle 100 also applies to options for a heating system ofthe separation vessel of the vehicle 200.

The separation system 120 may be configured to maintain a lower pressurein the separation vessel than a pressure maintained in the clathratestorage vessel 110. The separation system 120 may be configured tomaintain a pressure in the separation vessel sufficient to dissociate atleast some of the gas clathrates into the at least one gas and the hostmaterial and also maintain a pressure greater than the pressure requiredfor delivering fuel to the engine 130.

The separation system 120 may be configured to maintain an internalpressure in the separation vessel of about ambient pressure to about 30bar. Separation system 120 may be configured to maintain an internalpressure in the separation vessel of about 5 bar to about 20 bar.Separation system 120 may be configured to maintain an internal pressurein the separation vessel of about 10 bar to about 15 bar. Separationsystem 120 may be configured to maintain an internal pressure in theseparation vessel of about ambient pressure to about 10 bar. Separationsystem 120 may be configured to maintain an internal pressure in theseparation vessel of about ambient pressure. The separation vessel maybe designed to leak or vent before burst.

The separation system 120 may further comprise a pressure reducing valveoperably connected to the clathrate storage vessel 110 and theseparation vessel, wherein the pressure reducing valve is configured toreduce the pressure of gas clathrates transferred from the clathratestorage vessel 110 to the separation vessel.

The separation vessel of the separation system 120 may comprise achamber configured to dissociate the gas clathrates into the at leastone gas and the host material. The separation vessel of the separationsystem 120 may comprise a conduit configured to continuously dissociatethe gas clathrates into the at least one gas and the host material.

The separation vessel of the separation system 120 may comprise a hostmaterial outlet configured for removing the host material from theseparation vessel.

The separation system 120 may further comprise a temperature monitoringsystem configured to monitor the internal temperature of the separationvessel. The separation system 120 may further comprise an emergencycooling system configured to rapidly cool the separation vessel. Theseparation system 120 may further comprise a pressure monitoring deviceoperably connected to the separation vessel and configured to monitor aninternal pressure of the separation vessel. The separation system 120may further comprise a pressure relief device operably connected to theseparation vessel and configured to reduce pressure within theseparation vessel. The separation system 120 may further comprise apressurizing device operably connected to the separation vessel andconfigured to maintain pressure within the separation vessel. Thedisclosure regarding options for a temperature monitoring system, anemergency cooling system, a pressure monitoring device, a pressurerelief device, and a pressurizing device for the separation system 10also apply to options for the same for the separation system 120.

The separation vessel of the separation system 120 may comprise a gasoutlet configured for removing dissociated at least one gas from theseparation vessel. The separation system 120 may further comprise acontrol valve operably connected to the gas outlet and to the engine130, wherein the control valve is configured to control release ofstored at least one gas from the separation vessel. The separationsystem 120 may further comprise a metering system configured to controlintroduction of stored at least one gas to the engine 130. The meteringsystem may comprise a gas flow meter configured to measure the flow rateof the stored at least one gas released from the separation vessel. Theseparation system 120 may further comprise a transport device configuredto transport the dissociated at least one gas from the separation vesselto the engine 130, wherein the transport device is operably connected tothe separation vessel and to the engine 130. The transport device may beconfigured to control the transport of the dissociated at least one gasbased on fuel requirements of the engine 130. The transport device maycomprise a compressor, including, but not limited to, a compressorexemplified in the disclosure regarding the separation system 20.

The vehicle 200 may further comprise a gas storage vessel configured tostore the dissociated at least one gas removed from the separationsystem 120, wherein the gas storage vessel is operably connected to theseparation system 120 and is operably connected to the engine 130. Insuch embodiments, the vehicle 200 may further comprise a control valveoperably connected to the gas storage vessel and to the engine 130,wherein the control valve is configured to control release of stored atleast one gas from the gas storage vessel. The vehicle 200 may furthercomprise a metering system configured to control introduction of storedat least one gas to the engine 130. The metering system may comprise agas flow meter configured to measure the flow rate of the stored atleast one gas released from the gas storage vessel. The vehicle 200 mayfurther comprise a transport device configured to transport thedissociated at least one gas from the gas storage vessel to the engine130, wherein the transport device is operably connected to the gasstorage vessel and to the engine 130. The transport device may beconfigured to control the transport of the dissociated at least one gasbased on fuel requirements of the engine 130. The transport device maycomprise a compressor, including, but not limited to, a compressorexemplified in the disclosure regarding the separation system 20.

The vehicle 200 may further comprise a control valve operably connectedto the separation system 120 and to the gas storage vessel, wherein thecontrol valve is configured to control release of stored at least onegas from the separation vessel. The vehicle 200 may further comprise ametering system configured to control introduction of stored at leastone gas from the separation system to the gas storage vessel. Themetering system may comprise a gas flow meter configured to measure theflow rate of the stored at least one gas released from the separationvessel. The vehicle 200 may further comprise a transport deviceconfigured to transport the dissociated at least one gas from theseparation vessel to the gas storage vessel, wherein the transportdevice is operably connected to the separation vessel and to the gasstorage vessel. The transport device may be configured to control thetransport of the dissociated at least one gas based on fuel requirementsof the engine 130. The transport device may comprise a compressor,including, but not limited to, a compressor exemplified in thedisclosure regarding the separation system 20.

The vehicle 200 may further comprise a cooling device configured toreduce the temperature of the dissociated at least one gas prior tointroduction of the dissociated at least one gas to the engine 130. Thecooling device may comprise a heat exchanger. The heat exchanger may beconfigured to be cooled by ambient air. The heat exchanger may beconfigured to be cooled by a coolant also used to cool the engine 130.The heat exchanger may be configured to be cooled by the clathratestorage vessel 110. The heat exchanger may be configured to be cooled bythe separation system 120. The cooling device may comprise arefrigerated coil configured to cool the at least one gas.

The vehicle 200 may further comprise a transport device configured totransport the dissociated at least one gas from the separation system120 to the engine 130, wherein the transport device is operablyconnected to the separation system 120 and to the engine 130. Thetransport device may be configured to control the transport of thedissociated at least one gas based on fuel requirements of the engine130. The transport device may comprise a compressor. Examples of acompressor include, but are not limited to, a centrifugal compressor, amixed-flow compressor, an axial-flow compressor, a reciprocatingcompressor, a rotary screw compressor, a rotary vane compressor, ascroll compressor, and a diaphragm compressor. In such embodiments, thevehicle 200 may further comprise a cooling device, such as the coolingdevice disclosed above, configured to reduce the temperature of thedissociated at least one gas prior to introduction of the dissociated atleast one gas to the engine 130.

The vehicle 200 may comprise a moisture-removal system configured toremove water from the dissociated at least one gas prior to introductionof the dissociated at least one gas to the engine 130. Themoisture-removal system may comprise, by way of non-limiting example, adehumidifier, a dryer, or a molecular sieve column. In some embodiments,the moisture-removal system is part of the separation system 120.

The separation system 120 may be configured to receive a continuoussupply of gas clathrates while the vehicle 200 is operating. Theseparation system 120 may be configured to periodically receive a batchof gas clathrates while the vehicle 200 is operating. The separationsystem 120 may be configured to receive a variable supply of gasclathrates based on fuel requirements of the engine 130. The separationsystem 120 may be configured to control the rate of dissociation of thegas clathrates based on fuel requirements of the engine 130.

The vehicle 200 may comprise a host material storage vessel configuredto supply host material to the clathrate formation system 140, whereinthe host material storage vessel is operably connected to the clathrateformation system 140. The vehicle 200 may comprise a transport deviceconfigured to transport host material from the host material storagevessel to the clathrate formation system 140. The transport device mayfurther be configured to transport host material from the separationsystem 120 to the host material storage vessel. The host materialstorage vessel may be configured to store previously unused hostmaterial.

The vehicle 200 may comprise a filter configured to separate non-carbonproducts from the exhaust stream.

The vehicle 200 may comprise a catalytic converter configured to convertcarbon monoxide and uncombusted hydrocarbons to carbon dioxide. Examplesof partially combusted hydrocarbons include hydrocarbons with one, two,or three carbons.

The clathrate formation system 140 may be configured to utilizecombustion produced water as at least a portion of the host material inthe formation of carbon dioxide clathrates. In addition to carbondioxide clathrates, the clathrate formation system 140 may be configuredto also form carbon monoxide clathrates and partially combustedhydrocarbon clathrates. For example, the clathrate formation system 140may be configured to control the pressure and temperature of the exhauststream and the host material sufficient to form partially combustedhydrocarbon clathrates with partially combusted hydrocarbons and hostmaterial, to form carbon monoxide clathrates with carbon monoxide andhost material, and/or to form carbon dioxide clathrates with carbondioxide and host material.

The clathrate formation system 140 may comprise a cooling systemconfigured to cool the exhaust stream. The cooling system may beoperably connected with the separation system 120 and may be configuredto transfer heat from the exhaust stream to the separation system 120.The cooling system may comprise a heat exchanger configured to transferheat from the exhaust stream to an external heat sink, such as ambientair.

The clathrate formation system 140 may comprise a pressurization system.The pressurization system may comprise a compressor. Examples of acompressor include, but are not limited to, a centrifugal compressor, amixed-flow compressor, an axial-flow compressor, a reciprocatingcompressor, a rotary screw compressor, a rotary vane compressor, ascroll compressor, and a diaphragm compressor.

The clathrate formation system 140 may comprise a formation vesseloperably connected to the clathrate storage vessel 110.

The clathrate formation system 140 may further comprise a carbon dioxideremoval system configured to separate carbon dioxide from the exhauststream and deliver the removed carbon dioxide to the formation vessel.The carbon dioxide removal system may comprise a removal vessel operablyconnected to the exhaust stream and the formation vessel.

The removal vessel may be configured to contact the exhaust stream withat least one separation fluid. The separation fluid may comprise achemical solvent. The separation fluid may comprise a physical solvent.Examples of the separation fluid include fluids comprising analkanolamine, a monoethanolamine, a diethanolamine, amethyldiethanolamine, a triethanolamine, and/or piperazine. Theseparation fluid may be a liquid. The separation fluid may comprise hostmaterial.

The vehicle 200 may further comprise a regeneration system configured toseparate carbon dioxide from the separation fluid and operably coupledto the removal vessel. The regeneration system may comprise aregeneration vessel operably coupled to the removal vessel andconfigured to heat the separation fluid. The regeneration vessel may beconfigured to operate on a batch basis. The regeneration vessel may beconfigured to operate on a continuous basis. The regeneration vessel maycomprise a tank. The regeneration vessel may comprise a conduit.

In some embodiments, the removal vessel is configured to contact theexhaust stream with an alkali carbonate, such as sodium carbonate and/orpotassium carbonate. In such embodiments, the vehicle 200 may furthercomprise a regeneration system configured to separate carbon dioxidefrom the alkali carbonate and operably coupled to the removal vessel.The regeneration system may comprise a regeneration vessel operablycoupled to the removal vessel and configured to heat the alkalicarbonate. The regeneration vessel may be configured to operate on abatch basis or on a continuous basis. The regeneration vessel maycomprise a tank and/or a conduit.

In some embodiments, the removal vessel comprises a membrane configuredto separate carbon dioxide from the exhaust stream. The membrane maycomprise a polymer, such as a cellulose acetate polymer, a polyimidepolymer, a polyamide polymer, a polycarbonate polymer, a polysulfonepolymer, and/or a polyetherimide polymer. The membrane may comprise flatsheets. The flat sheets may be spiral-wound. The membrane may comprisehollow fibers.

The removal vessel may be configured to operate on a batch basis. Forexample, the removal vessel may comprise a tank. The removal vessel maybe configured to operate on a continuous basis. For example, the removalvessel may comprise a conduit.

The clathrate formation system 140 may be configured to control the rateof formation of the carbon dioxide clathrates by regulating at least oneof the temperature and the pressure of exhaust gases within theformation vessel. The formation vessel may be configured to operate at atemperature and/or a pressure that is about the same as an operatingtemperature of the clathrate storage vessel 110.

The formation vessel may further comprise insulation configured tomaintain an internal temperature of the formation vessel. The insulationmay comprise at least one material configured to and compatible withmaintaining desired temperatures within the formation vessel. Examplesof such materials include, but are not limited to, calcium silicate,cellular glass, elastomeric foam, fiberglass, polyisocyanurate,polystyrene, and polyurethane. The insulation may comprise at least onevacuum layer and/or multi-layer insulation. The insulation mayreleasably surround at least a portion of an outer surface of the vesseland/or the insulation may be attached to at least a portion of a surfaceof the vessel, including an outer and/or inner surface.

The vehicle 200 may further comprise a refrigeration system configuredto maintain an internal temperature of the formation vessel within a setrange. The refrigeration system may also be configured to cool theexhaust stream. The refrigeration system may be integrated with arefrigeration system of the clathrate storage vessel 110, if present.The set range may be from about 0 degrees Centigrade to about 25 degreesCentigrade, including from about 0 degrees Centigrade to about 20degrees Centigrade, including from about 0 degrees Centigrade to about15 degrees Centigrade, including from about 0 degrees Centigrade toabout 10 degrees Centigrade, and including from about 4 degreesCentigrade to about 10 degrees Centigrade.

The refrigeration system may comprise a heat pipe configured and locatedto control the temperature of the formation vessel. The heat pipe may beoperably connected to the separation system. The refrigeration systemmay also comprise a vapor compression system. The vapor compressionsystem may utilize a chlorofluorocarbon, a chlorofluoroolefin, ahydrochlorofluorocarbon, a hydrochloro-fluoroolefin, ahydrofluoroolefin, a hydrochloroolefin, a hydroolefin, a hydrocarbon, aperfluoroolefin, a perfluorocarbon, a perchloroolefin, aperchlorocarbon, and/or a halon. The refrigeration system may comprise avapor absorption system. The vapor absorption system may utilize water,ammonia, and/or lithium bromide. The refrigeration system may comprise agas cycle refrigeration system, such as one that utilizes air. Therefrigeration system may comprise a stirling cycle refrigeration system.The stirling cycle refrigeration system may utilize helium. The stirlingcycle refrigeration system may comprise a free piston stirling cooler.The refrigeration system may comprise a thermoelectric refrigerationsystem.

The clathrate formation system 140 may be configured to generate aninternal pressure in the formation vessel of about ambient pressure toabout 30 bar, an internal pressure of about 10 bar to about 30 bar, aninternal pressure of about 10 bar to about 15 bar, an internal pressureof about 15 bar to about 27 bar, or an internal pressure of about 20 barto about 27 bar. The formation vessel may be designed to leak or ventbefore burst. Each of the vessels may independently further comprise apressure relief device operably connected to the vessel and configuredto reduce pressure within the vessel. Examples of a pressure reliefdevice include, but are not limited to, a pressure relief valve and arupture disc.

The clathrate formation system 140 may be configured to pressurize theexhaust stream in the formation vessel without substantially increasingback pressure on the exhaust ports of the engine 130. In suchembodiments, the clathrate formation system 140 may comprise a valveoperably connected to the formation vessel, wherein the valve isconfigured to control introduction of the exhaust stream to theformation vessel. The clathrate formation system 140 may be configuredto sequentially introduce batches of the exhaust stream to the formationvessel. For example, introduction of the exhaust stream batches to theformation vessel may be timed to coincide with the closing of exhaustports of the engine 130.

The clathrate formation system 140 may further comprise at least oneholding vessel for temporarily storing the exhaust stream at a lowpressure prior to introduction of the exhaust stream to the formationvessel for pressurizing. The low pressure may be less than the pressureat which carbon dioxide clathrates are formed in the formation vessel.The low pressure may be substantially equal to what the pressure of theexhaust stream at an exhaust port of the engine 130 would be if theclathrate formation system 140 and clathrate storage vessel 110 were notconnected to the engine 130. The low pressure may be about equal toatmospheric pressure.

The clathrate formation system 140 may comprise a compressor, wherein aninlet of the compressor is operably connected to exhaust ports of theengine 130 and an outlet of the compressor is operably connected to theformation vessel. The compressor may be configured to reduce backpressure on exhaust ports of the engine 130 to be substantially equal towhat the pressure at the exhaust ports would be if the clathrateformation system 140 and clathrate storage vessel 110 were not connectedto the exhaust stream. The compressor may be configured to minimize backpressure on the exhaust ports of the engine 130 while pressurizing theformation vessel. Examples of a compressor include, but are not limitedto, a centrifugal compressor, a mixed-flow compressor, an axial-flowcompressor, a reciprocating compressor, a rotary screw compressor, arotary vane compressor, a scroll compressor, and a diaphragm compressor.

The formation vessel may comprise a chamber configured to form batchesof carbon dioxide clathrates and/or the formation vessel may comprise aconduit operably connected to the clathrate storage vessel 110 andconfigured to continuously form carbon dioxide clathrates.

The clathrate formation system 140 may comprise a moveable pressintegrated with the formation vessel and configured to pressurize theformation vessel. For example, the moveable press may include, but isnot limited to, a hydraulic press or an electromagnetically activatedpress.

The clathrate formation system 140 may further comprise a temperaturemonitoring system configured to monitor the internal temperature of theformation vessel. The temperature monitoring system may comprise athermostat, a thermistor, a thermocouple, and/or a resistive temperaturedetector.

The clathrate formation system 140 may further comprise a pressuremonitoring device operably connected to the formation vessel andconfigured to monitor an internal pressure of the formation vessel. Forexample, the pressure monitoring device may comprise a piezoresistivestrain gauge, a capacitive sensor, an electromagnetic sensor, apiezoelectric sensor, an optical sensor, a potentiometric sensor, athermal conductivity sensor, and/or an ionization sensor.

The clathrate formation system 140 may further comprise a pressurerelief device operably connected to the formation vessel and configuredto reduce pressure within the formation vessel. Examples of a pressurerelief device include, but are not limited to, a pressure relief valveand a rupture disc.

The vehicle 200 may further comprise a transport device operablyconnected to the clathrate storage vessel 110, operably connected to theformation vessel, and operably connected to the separation vessel,wherein the transport device is configured to transfer gas clathratesfrom the clathrate storage vessel 110 to the separation vessel and isalso configured to transfer carbon dioxide clathrates from the formationvessel to the clathrate storage vessel 110.

The transport device may comprise a moveable surface, such as a conveyorbelt, a rotating drum, a string, and/or a rotating disk. The moveablesurface may comprise a high-surface-area material, such as thehigh-surface-area materials disclosed above for the fuel storage vessel10. The transport device may be configured to transport the gasclathrates and carbon dioxide clathrates as a solid.

The vehicle 200 may further comprise a tracking system configured tomonitor the position of the moveable surface to determine whichclathrates comprise gas clathrates and which clathrates comprise carbondioxide clathrates. The tracking system may comprise an optical trackingsystem, a mechanical tracking system, a magnetic sensor, and/or a halleffect sensor.

Additionally, the separation system 120 may be configured to dissociatesubstantially all of the gas clathrates located on a portion of themoveable surface transported to the separation system 120, such thatwhen that portion of the moveable surface is transported to theclathrate formation system 140, then that portion of the moveablesurface is substantially free from gas clathrates.

Alternatively, the vehicle 200 may further comprise a transport deviceoperably connected to the clathrate storage vessel 140 and operablyconnected to the formation vessel and configured to transfer carbondioxide clathrates from the formation vessel to the clathrate storagevessel 140. In this embodiment, the transport device is independent ofthe separation vessel. In this embodiment, the transport device may alsocomprise a moveable surface, such as a conveyor belt, a rotating drum, astring, and/or a rotating disk. The moveable surface may comprise ahigh-surface-area material, such as the high-surface-area materialsdisclosed above for the fuel storage vessel 10. The transport device maybe configured to transport the carbon dioxide clathrates as a slurryand/or as a solid, such as solid chunks or pellets.

The transport device may be at least partially located internally withinthe formation vessel. Likewise, the transport device may be at leastpartially external to the formation vessel. Accordingly, the transportdevice may be at least partially integrated into a portion of a surface,including an internal or external surface, of the formation vessel.Additionally, the transport device may be at least partially integratedinto a portion of a surface, including an internal or external surface,of the clathrate storage vessel 110. Likewise, the transport device maybe at least partially internal and/or external to the clathrate storagevessel 110.

The transport device may be configured for moving solid carbon dioxideclathrate. The transport device may be configured for moving carbondioxide clathrate slurry. The transport device may be configured to behydraulically, mechanically, and/or electrically actuated.

The transport device may comprise an extruder and/or a pump. When thetransport device comprises a pump, the inlet of the pump may be operablyconnected to the formation vessel and an outlet of the pump may beoperably connected to the clathrate storage vessel 110. Examples of thepump include, but are not limited to, a positive displacement pump, alobe pump, an external gear pump, an internal gear pump, a peristalticpump, a screw pump, a progressive cavity pump, a flexible impeller pump,a rotary vane pump, and a centrifugal pump. The pump may be any pumpcompatible with pumping a carbon dioxide clathrate slurry.

The clathrate formation system 140 may be configured to receive acontinuous supply of carbon dioxide or may be configured to periodicallyreceive a batch of carbon dioxide, while the vehicle 200 is operating.The clathrate formation system 40 may be configured to receive avariable supply of the exhaust stream based on the quantity of exhaustproduced by the engine 130.

The clathrate storage vessel 110 may be configured to receive the carbondioxide clathrates as a solid and/or as a slurry.

The clathrate storage vessel 110 may be configured for removal of storedcarbon dioxide from the vehicle 200 when the vehicle 200 is otherwisenot in use. The clathrate storage vessel 110 may be configured to reducethe pressure and/or increase the temperature of the clathrate storagevessel 110 sufficient to dissociate the stored carbon dioxide clathratesinto carbon dioxide and host material. For example, the clathratestorage vessel 110 may be configured to sufficiently warm stored carbondioxide clathrates so as to liquefy the host material and gasify thecarbon dioxide. The clathrate storage vessel 110 may comprise an outletconfigured for removal of dissociated carbon dioxide. The clathratestorage vessel 110 may also comprise an outlet configured for removal ofdissociated host material.

The vehicle 200 may further comprise a heating system configured andlocated to impart heat energy to the clathrate storage vessel 110. Theheating system may be located internal or external to the vessel. Forexample, the heating system may be integrated into or attached to aportion of a surface of the clathrate storage vessel 110, includingexternal or internal surfaces. The heating system may be independentlyconfigured to transfer heat energy from the coolant used to cool theengine 130. Likewise, the heating system may be configured to transferheat energy from heat generated by the engine 130 in any fashion, suchas from an exhaust stream generated by the engine 130. For example, theheating system may be configured to divert the exhaust stream from theclathrate formation system 140 and also configured to transfer heat fromthe diverted exhaust stream to the clathrate storage vessel 110. In thatexample, the heating system may be further configured to divert theexhaust stream from the clathrate storage vessel 110 and vent theexhaust stream to atmosphere. Alternatively or in addition thereto, theheating system may utilize solar energy, ambient temperatures, electricresistance heating elements, microwave heating, electromagnetic heating,and/or dielectric heating to impart heat energy.

The clathrate storage vessel 110 may be configured for removal of solidand/or slurry carbon dioxide clathrates from the clathrate storagevessel 110.

The clathrate storage vessel 110 may be configured to maintain carbondioxide clathrates as a solid and/or slurry until removal of carbondioxide from the vehicle 200 is intended.

The vehicle 200 may comprise a dissociation vessel operably connected tothe clathrate storage vessel 110 and configured to receive carbondioxide clathrates from the clathrate storage vessel 110. Thedissociation vessel may be configured for removal of stored carbondioxide from the vehicle 200 when the vehicle 200 is otherwise not inuse. The dissociation vessel may be configured to reduce the pressureand/or increase the temperature of the dissociation vessel sufficient todissociate the stored carbon dioxide clathrates into carbon dioxide andhost material.

The vehicle 200 may further comprise a recycle system configured totransfer dissociated host material from the separation system 120 to theclathrate formation system 140. The recycle system may further comprisea host material storage vessel configured to store dissociated hostmaterial from the separation system 120. The recycle system may comprisea transfer device configured to transfer the dissociated host materialto the clathrate formation system 140. The recycle system may comprise afilter configured to clean dissociated host material prior to transferof the dissociated host material to the clathrate formation system 140;e.g., to remove a clathrate stabilizer more suitable for gas clathratesthan for carbon dioxide clathrates. The recycle system may comprise asupply reservoir configured to add a component to the host materialprior to transfer of the dissociated host material to the clathrateformation system 140; e.g., to add a clathrate stabilizer more suitablefor carbon dioxide clathrates than for gas clathrates.

FIGS. 1 and 2 illustrate vehicles that utilize gas clathrates to storefuel for the vehicles. FIG. 3 illustrates an additional embodiment of avehicle with reduced emissions, but where gas clathrates are not used tostore the fuel for the vehicle. FIG. 3 illustrates a vehicle with aconventional fuel source, such as gasoline or diesel, that utilizesclathrates to capture carbon dioxide emissions. FIG. 3 illustrates avehicle 300 comprising a clathrate formation system 240 and an exhauststorage vessel 250. Accordingly, the disclosure regarding the clathrateformation system 40 and the exhaust storage vessel 50 may apply to theclathrate formation system 240 and the exhaust storage vessel 250 of thevehicle 300 and vice versa.

The vehicle 300 comprises an engine 230, a supply of host material, aclathrate formation system 240 operably connected to the engine 230,operably connected to the supply of host material, and configured tocombine carbon dioxide from an exhaust stream from the engine with thehost material to form carbon dioxide clathrates. The vehicle 300 mayfurther comprise an exhaust storage vessel configured to store carbondioxide clathrates.

The vehicle 300 may be any number of conventional vehicles, such as, forexample, a locomotive, a tractor configured for attachment to asemi-trailer, a bus, a car, or a pick-up truck. The engine 230 may beany number of conventional engines, such as, for example, a gasolineengine, a diesel engine, or a natural gas engine.

The disclosure regarding the host materials of the vehicles 100 and 200applies equally to the host material of the vehicle 300. The vehicle 300may further comprise a host material storage vessel 260 configured tosupply host material to the clathrate formation system 240, wherein thehost material storage vessel 260 is operably connected to the clathrateformation system 240. The vehicle 300 may further comprise a transportdevice configured to transport host material from the host materialstorage vessel 260 to the clathrate formation system 240. The hostmaterial storage vessel 260 may be configured to receive previouslyunused and/or recycled host material.

The vehicle 300 may comprise a filter configured to separate non-carbonproducts from the exhaust stream.

The vehicle 300 may comprise a catalytic converter configured to convertcarbon monoxide and uncombusted hydrocarbons to carbon dioxide.

The clathrate formation system 240 may be configured to utilizecombustion produced water as at least a portion of the host material inthe formation of carbon dioxide clathrates. In addition to carbondioxide clathrates, the clathrate formation system 240 may be configuredto also form carbon monoxide clathrates and partially combustedhydrocarbon clathrates. For example, the clathrate formation system 240may be configured to control the pressure and temperature of the exhauststream and the host material sufficient to form partially combustedhydrocarbon clathrates with partially combusted hydrocarbons and hostmaterial, to form carbon monoxide clathrates with carbon monoxide andhost material, and/or to form carbon dioxide clathrates with carbondioxide and host material. Likewise, the exhaust storage vessel 250 mayalso be configured to form carbon monoxide clathrates and partiallycombusted hydrocarbon clathrates in addition to carbon dioxideclathrates.

The clathrate formation system 240 may comprise a cooling systemconfigured to cool the exhaust stream. The cooling system may comprise aheat exchanger configured to transfer heat from the exhaust stream to anexternal heat sink, such as ambient air.

The clathrate formation system 240 may comprise a pressurization system.The pressurization system may comprise a compressor. Examples of acompressor include, but are not limited to, a centrifugal compressor, amixed-flow compressor, an axial-flow compressor, a reciprocatingcompressor, a rotary screw compressor, a rotary vane compressor, ascroll compressor, and a diaphragm compressor.

The clathrate formation system 240 may comprise a formation vesseloperably connected to the exhaust storage vessel 250.

The clathrate formation system 240 may further comprise a carbon dioxideremoval system configured to separate carbon dioxide from the exhauststream and deliver the removed carbon dioxide to the formation vessel.The carbon dioxide removal system may comprise a removal vessel operablyconnected to the exhaust stream and the formation vessel.

The removal vessel may be configured to contact the exhaust stream withat least one separation fluid. The separation fluid may comprise achemical solvent. The separation fluid may comprise a physical solvent.Examples of the separation fluid include fluids comprising analkanolamine, a monoethanolamine, a diethanolamine, amethyldiethanolamine, a triethanolamine, and/or piperazine. Theseparation fluid may be a liquid. The separation fluid may comprise hostmaterial.

The vehicle 300 may further comprise a regeneration system configured toseparate carbon dioxide from the separation fluid and operably coupledto the removal vessel. The regeneration system may comprise aregeneration vessel operably coupled to the removal vessel andconfigured to heat the separation fluid. The regeneration vessel may beconfigured to operate on a batch basis. The regeneration vessel may beconfigured to operate on a continuous basis. The regeneration vessel maycomprise a tank. The regeneration vessel may comprise a conduit.

In some embodiments, the removal vessel is configured to contact theexhaust stream with an alkali carbonate, such as sodium carbonate and/orpotassium carbonate. In such embodiments, the vehicle 300 may furthercomprise a regeneration system configured to separate carbon dioxidefrom the alkali carbonate and operably coupled to the removal vessel.The regeneration system may comprise a regeneration vessel operablycoupled to the removal vessel and configured to heat the alkalicarbonate. The regeneration vessel may be configured to operate on abatch basis or on a continuous basis. The regeneration vessel maycomprise a tank and/or a conduit.

In some embodiments, the removal vessel comprises a membrane configuredto separate carbon dioxide from the exhaust stream. The membrane maycomprise a polymer, such as a cellulose acetate polymer, a polyimidepolymer, a polyamide polymer, a polycarbonate polymer, a polysulfonepolymer, and/or a polyetherimide polymer. The membrane may comprise flatsheets. The flat sheets may be spiral-wound. The membrane may comprisehollow fibers.

The removal vessel may be configured to operate on a batch basis. Forexample, the removal vessel may comprise a tank. The removal vessel maybe configured to operate on a continuous basis. For example, the removalvessel may comprise a conduit.

The clathrate formation system 240 may be configured to control the rateof formation of the carbon dioxide clathrates by regulating at least oneof the temperature and the pressure of exhaust gases within theformation vessel. The formation vessel may further comprise insulationconfigured to maintain an internal temperature of the formation vessel.The insulation may comprise at least one material configured to andcompatible with maintaining desired temperatures within the formationvessel. Examples of such materials include, but are not limited to,calcium silicate, cellular glass, elastomeric foam, fiberglass,polyisocyanurate, polystyrene, and polyurethane. The insulation maycomprise at least one vacuum layer and/or multi-layer insulation. Theinsulation may releasably surround at least a portion of an outersurface of the vessel and/or the insulation may be attached to at leasta portion of a surface of the vessel, including an outer and/or innersurface.

The vehicle 300 may further comprise a refrigeration system configuredto maintain an internal temperature of the formation vessel within a setrange. The refrigeration system may also be configured to cool theexhaust stream. The set range may be from about 0 degrees Centigrade toabout 25 degrees Centigrade, including from about 0 degrees Centigradeto about 20 degrees Centigrade, including from about 0 degreesCentigrade to about 15 degrees Centigrade, including from about 0degrees Centigrade to about 10 degrees Centigrade, and including fromabout 4 degrees Centigrade to about 10 degrees Centigrade.

The refrigeration system may comprise a heat pipe configured and locatedto control the temperature of the formation vessel. The refrigerationsystem may also comprise a vapor compression system. The vaporcompression system may utilize a chlorofluorocarbon, achlorofluoroolefin, a hydrochlorofluorocarbon, ahydrochloro-fluoroolefin, a hydrofluoroolefin, a hydrochloroolefin, ahydroolefin, a hydrocarbon, a perfluoroolefin, a perfluorocarbon, aperchloroolefin, a perchlorocarbon, and/or a halon. The refrigerationsystem may comprise a vapor absorption system. The vapor absorptionsystem may utilize water, ammonia, and/or lithium bromide. Therefrigeration system may comprise a gas cycle refrigeration system, suchas one that utilizes air. The refrigeration system may comprise astirling cycle refrigeration system. The stirling cycle refrigerationsystem may utilize helium. The stirling cycle refrigeration system maycomprise a free piston stirling cooler. The refrigeration system maycomprise a thermoelectric refrigeration system.

The clathrate formation system 240 may be configured to generate aninternal pressure in the formation vessel of about ambient pressure toabout 30 bar, an internal pressure of about 10 bar to about 30 bar, aninternal pressure of about 10 bar to about 15 bar, an internal pressureof about 15 bar to about 27 bar, or an internal pressure of about 20 barto about 27 bar. The formation vessel may be designed to leak or ventbefore burst. The formation vessel may further comprise a pressurerelief device operably connected to the vessel and configured to reducepressure within the vessel. Examples of a pressure relief deviceinclude, but are not limited to, a pressure relief valve and a rupturedisc.

The clathrate formation system 240 may be configured to pressurize theexhaust stream in the formation vessel without substantially increasingback pressure on the exhaust ports of the engine 230. In suchembodiments, the clathrate formation system 240 may comprise a valveoperably connected to the formation vessel, wherein the valve isconfigured to control introduction of the exhaust stream to theformation vessel. The clathrate formation system 240 may be configuredto sequentially introduce batches of the exhaust stream to the formationvessel. For example, introduction of the exhaust stream batches to theformation vessel may be timed to coincide with the closing of exhaustports of the engine 230.

The clathrate formation system 240 may further comprise at least oneholding vessel for temporarily storing the exhaust stream at a lowpressure prior to introduction of the exhaust stream to the formationvessel for pressurizing. The low pressure may be less than the pressureat which carbon dioxide clathrates are formed in the formation vessel.The low pressure may be substantially equal to what the pressure of theexhaust stream at an exhaust port of the engine 230 would be if theclathrate formation system 240 and the exhaust storage vessel 250 werenot connected to the engine 230. The low pressure may be about equal toatmospheric pressure.

The clathrate formation system 240 may comprise a compressor, wherein aninlet of the compressor is operably connected to exhaust ports of theengine 230 and an outlet of the compressor is operably connected to theformation vessel. The compressor may be configured to reduce backpressure on exhaust ports of the engine 230 to be substantially equal towhat the pressure at the exhaust ports would be if the clathrateformation system 240 and exhaust storage vessel 250 were not connectedto the exhaust stream. The compressor may be configured to minimize backpressure on the exhaust ports of the engine 230 while pressurizing theformation vessel. Examples of a compressor include, but are not limitedto, a centrifugal compressor, a mixed-flow compressor, an axial-flowcompressor, a reciprocating compressor, a rotary screw compressor, arotary vane compressor, a scroll compressor, and a diaphragm compressor.

The formation vessel may comprise a chamber configured to form batchesof carbon dioxide clathrates and/or the formation vessel may comprise aconduit operably connected to the exhaust storage vessel 250 andconfigured to continuously form carbon dioxide clathrates.

The clathrate formation system 240 may comprise a moveable pressintegrated with the formation vessel and configured to pressurize theformation vessel. For example, the moveable press may include, but isnot limited to, a hydraulic press or an electromagnetically activatedpress.

The clathrate formation system 240 may further comprise a temperaturemonitoring system configured to monitor the internal temperature of theformation vessel. The temperature monitoring system may comprise athermostat, a thermistor, a thermocouple, and/or a resistive temperaturedetector.

The clathrate formation system 240 may further comprise a pressuremonitoring device operably connected to the formation vessel andconfigured to monitor an internal pressure of the formation vessel. Forexample, the pressure monitoring device may comprise a piezoresistivestrain gauge, a capacitive sensor, an electromagnetic sensor, apiezoelectric sensor, an optical sensor, a potentiometric sensor, athermal conductivity sensor, and/or an ionization sensor.

The clathrate formation system 240 may further comprise a pressurerelief device operably connected to the formation vessel and configuredto reduce pressure within the formation vessel. Examples of a pressurerelief device include, but are not limited to, a pressure relief valveand a rupture disc.

The vehicle 300 may further comprise a transport device operablyconnected to the formation vessel and the exhaust storage vessel andconfigured to transfer carbon dioxide clathrates from the formationvessel to the exhaust storage vessel. The transport device may beconfigured to transport the carbon dioxide clathrates as a slurry and/oras a solid, such as solid chunks or pellets.

The transport device may be at least partially located internally withinthe formation vessel. Likewise, the transport device may be at leastpartially external to the formation vessel. Accordingly, the transportdevice may be at least partially integrated into a portion of a surface,including an internal or external surface, of the formation vessel.Additionally, the transport device may be at least partially integratedinto a portion of a surface, including an internal or external surface,of the exhaust storage vessel 250. Likewise, the transport device may beat least partially internal and/or external to the exhaust storagevessel 250.

The transport device may be configured for moving solid carbon dioxideclathrate. The transport device may be configured for moving carbondioxide clathrate slurry. The transport device may be configured to behydraulically, mechanically, and/or electrically actuated.

The transport device may comprise an extruder and/or a pump. When thetransport device comprises a pump, the inlet of the pump may be operablyconnected to the formation vessel and an outlet of the pump may beoperably connected to the exhaust storage vessel 250. Examples of thepump include, but are not limited to, a positive displacement pump, alobe pump, an external gear pump, an internal gear pump, a peristalticpump, a screw pump, a progressive cavity pump, a flexible impeller pump,a rotary vane pump, and a centrifugal pump. The pump may be any pumpcompatible with pumping a carbon dioxide clathrate slurry.

The clathrate formation system 240 may be integrated with the exhauststorage vessel 250. The clathrate formation system 240 may be configuredto form carbon dioxide clathrates by regulating at least one of thetemperature and the pressure of carbon dioxide and host material withinthe exhaust storage vessel 250 to be compatible with forming carbondioxide clathrates. For example, the temperature may be regulated to beabout 0 degrees Centigrade to about 25 degrees Centigrade, may beregulated to be about 0 degrees Centigrade to about 20 degreesCentigrade, may be regulated to be about 0 degrees Centigrade to about15 degrees Centigrade, may be regulated to be about 0 degrees Centigradeto about 10 degrees Centigrade, or may be regulated to be about 4degrees Centigrade to about 10 degrees Centigrade. In another example,the pressure may be regulated to be about 1 bar to about 30 bar, thepressure may be regulated to be about 10 bar to about 30 bar, thepressure may be regulated to be about 10 bar to about 15 bar, thepressure may be regulated to be about 15 bar to about 27 bar, or thepressure may be regulated to be about 20 bar to about 27 bar.

Likewise, the exhaust storage vessel 250 may be configured to agitatethe carbon dioxide and the host material at a temperature and a pressurecompatible with forming the carbon dioxide clathrates. For example, theexhaust storage vessel 250 may comprise a mixing element located withinthe exhaust storage vessel 250 and configured to agitate the carbondioxide and the host material.

Additionally, the exhaust storage vessel 250 may comprisehigh-surface-area materials configured for forming carbon dioxideclathrates on the surface thereof. By way of non-limiting example, thehigh-surface-area material may comprise a graphene-based material, anactivated carbon, and/or a metal organic framework, such as a bidentatecarboxylic comprising ligand, a tridentate carboxylic comprising ligand,an azole comprising ligand, or a squaric acid comprising ligand.

The clathrate formation system 240 may further comprise a heat pipeconfigured and located to modulate the temperature of the exhauststorage vessel 250.

The clathrate formation system 240 may be configured to receive acontinuous supply of carbon dioxide or may be configured to periodicallyreceive a batch of carbon dioxide, while the vehicle 300 is operating.The clathrate formation system 240 may be configured to receive avariable supply of the exhaust stream based on the quantity of exhaustproduced by the engine 230.

The exhaust storage vessel 250 may be configured to receive the carbondioxide clathrates as a solid and/or as a slurry.

The exhaust storage vessel 250 may be configured for removal of storedcarbon dioxide from the vehicle 300 when the vehicle 300 is otherwisenot in use. The exhaust storage vessel 250 may be configured to reducethe pressure and/or increase the temperature of the exhaust storagevessel 250 sufficient to dissociate the stored carbon dioxide clathratesinto carbon dioxide and host material. For example, the exhaust storagevessel 250 may be configured to sufficiently warm stored carbon dioxideclathrates so as to liquefy the host material and gasify the carbondioxide. The exhaust storage vessel 250 may comprise an outletconfigured for removal of dissociated carbon dioxide. The exhauststorage vessel 250 may also comprise an outlet configured for removal ofdissociated host material.

Vehicle 300 may further comprise a heating system configured and locatedto impart heat energy to the exhaust storage vessel 250. The heatingsystem may be located internal or external to the vessel. For example,the heating system may be integrated into or attached to a portion of asurface of the exhaust storage vessel 250, including external orinternal surfaces. The heating system may be independently configured totransfer heat energy from the coolant used to cool the engine 230.Likewise, the heating system may be configured to transfer heat energyfrom heat generated by the engine 230 in any fashion, such as from anexhaust stream generated by the engine 230. For example, the heatingsystem may be configured to divert the exhaust stream from the clathrateformation system 240 and also configured to transfer heat from thediverted exhaust stream to the exhaust storage vessel 250. In thatexample, the heating system may be further configured to divert theexhaust stream from the exhaust storage vessel 250 and vent the exhauststream to atmosphere. Alternatively or in addition thereto, the heatingsystem may utilize solar energy, ambient temperatures, electricresistance heating elements, microwave heating, electromagnetic heating,and/or dielectric heating to impart heat energy.

The vehicle 300 may further comprise a recycle system configured totransfer dissociated host material from the exhaust storage vessel 250to the host material storage vessel 260. The recycle system may comprisea filter configured to clean dissociated host material prior to transferof the dissociated host material to the host material storage vessel260. The recycle system may comprise a transfer device configured totransfer the dissociated host material to the host material storagevessel 260.

The exhaust storage vessel 250 may be configured for removal of solidand/or slurry carbon dioxide clathrates from the exhaust storage vessel250.

The exhaust storage vessel 250 may be configured to maintain carbondioxide clathrates as a solid and/or slurry until removal of carbondioxide from the vehicle 300 is intended.

The exhaust storage vessel 250 may be configured to be detachable andreattachable from the remainder of the vehicle 300. For example, theexhaust storage vessel 250 may be configured to be exchanged with adifferent exhaust storage vessel 250 that has been emptied of carbondioxide clathrates.

The vehicle 300 may further comprise a sensor configured to monitor theamount of carbon dioxide clathrates in the exhaust storage vessel 250.The sensor may be configured to measure a mass of the carbon dioxideclathrates. The sensor may be configured to measure a vapor pressure ofcarbon dioxide gas present in the exhaust storage vessel 250. The sensormay be configured to determine a concentration of carbon dioxide presentin the exhaust storage vessel 250. The sensor may be configured tomonitor the amount of carbon dioxide removed from the exhaust storagevessel 250.

The vehicle 300 may alternatively comprise a dissociation vesseloperably connected to the exhaust storage vessel 250 and configured toreceive carbon dioxide clathrates from the exhaust storage vessel 250.The dissociation vessel may be configured for removal of stored carbondioxide from the vehicle 300 when the vehicle 300 is otherwise not inuse. The dissociation vessel may be configured to reduce the pressureand/or increase the temperature of the dissociation vessel sufficient todissociate the stored carbon dioxide clathrates into carbon dioxide andhost material.

The vehicle 300 may further comprise a temperature monitoring systemconfigured to monitor the internal temperature of the exhaust storagevessel 250. The temperature monitoring system may comprise a thermostat,a thermistor, a thermocouple, and/or a resistive temperature detector.

The vehicle 300 may further comprise a control system configured tomonitor both pressure and temperature of the exhaust storage vessel 250and configured to regulate at least one of pressure and temperature inorder to maintain the carbon dioxide clathrate within a clathratestability range.

The exhaust storage vessel 250 may comprise insulation. The insulationmay comprise at least one material configured to and compatible withmaintaining desired temperatures within each vessel. Examples of suchmaterials include, but are not limited to, calcium silicate, cellularglass, elastomeric foam, fiberglass, polyisocyanurate, polystyrene, andpolyurethane. The insulation may comprise at least one vacuum layerand/or multi-layer insulation. The insulation may releasably surround atleast a portion of an outer surface of the vessel and/or the insulationmay be attached to at least a portion of a surface of the vessel,including an outer and/or inner surface.

The exhaust storage vessel 250 may comprise a refrigeration systemconfigured to maintain an internal temperature of about 0 degreesCentigrade to about 25 degrees Centigrade. The exhaust storage vessel250 may be configured to maintain an internal temperature of about 0degrees Centigrade to about 20 degrees Centigrade. The exhaust storagevessel 250 may be configured to maintain an internal temperature ofabout 0 degrees Centigrade to about 15 degrees Centigrade. The exhauststorage vessel 250 may be configured to maintain an internal temperatureof about 0 degrees Centigrade to about 10 degrees Centigrade, includingfrom about 4 degrees Centigrade to about 10 degrees Centigrade.

The refrigeration system may comprise a heat pipe. The refrigerationsystem may also comprise a vapor compression system. The vaporcompression system may utilize a chlorofluorocarbon, achlorofluoroolefin, a hydrochlorofluorocarbon, ahydrochloro-fluoroolefin, a hydrofluoroolefin, a hydrochloroolefin, ahydroolefin, a hydrocarbon, a perfluoroolefin, a perfluorocarbon, aperchloroolefin, a perchlorocarbon, and/or a halon. The refrigerationsystem may comprise a vapor absorption system. The vapor absorptionsystem may utilize water, ammonia, and/or lithium bromide. Therefrigeration system may comprise a gas cycle refrigeration system, suchas one that utilizes air. The refrigeration system may comprise astirling cycle refrigeration system. The stirling cycle refrigerationsystem may utilize helium. The stirling cycle refrigeration system maycomprise a free piston stirling cooler. The refrigeration system maycomprise a thermoelectric refrigeration system.

The formation vessel, if present, and the exhaust storage vessel 250 mayeach be comprised of structural materials configured to and compatiblewith maintaining desired temperatures and pressures within eachrespective vessel. The structural material may comprise aluminum, brass,copper, ferretic steel, carbon steel, stainless steel,polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE),vinylidene polyfluoride (PVDF), polyamide (PA), polypropylene (PP),nitrile rubber (NBR), chloroprene (CR), chlorofluorocarbons (FKM),and/or composite materials, including composite materials comprisingcarbon fibers, glass fibers, and/or aramid fibers.

The exhaust storage vessel 250 may be designed to maintain an internalpressure of about 1 bar to about 30 bar, an internal pressure of about10 bar to about 30 bar, an internal pressure of about 10 bar to about 15bar, an internal pressure of about 15 bar to about 27 bar, an internalpressure of about 20 bar to about 27 bar. The vessel may be designed toleak or vent before burst. The vessel may further comprise a pressurerelief device operably connected to the vessel and configured to reducepressure within the vessel. Examples of a pressure relief deviceinclude, but are not limited to, a pressure relief valve and a rupturedisc.

The vehicle 300 may further comprise a pressurizing device operablyconnected to the exhaust storage vessel 250 and configured to maintainpressure within the exhaust storage vessel 250. Examples of apressurizing device include a moveable press integrated with the vessel,wherein the moveable press is configured to maintain pressure within thevessel. For example, the moveable press may include, but is not limitedto, a hydraulic press or an electromagnetically activated press. Inother examples, the pressurizing device may comprise a compressor.Examples of a compressor include, but are not limited to, a centrifugalcompressor, a mixed-flow compressor, an axial-flow compressor, areciprocating compressor, a rotary screw compressor, a rotary vanecompressor, a scroll compressor, and a diaphragm compressor.

Vehicle 300 may further comprise a pressure monitoring device operablyconnected to the exhaust storage vessel 250 and configured to monitor aninternal pressure of the exhaust storage vessel 250. The pressuremonitoring device may comprise a piezoresistive strain gauge, acapacitive sensor, an electromagnetic sensor, a piezoelectric sensor, anoptical sensor, a potentiometric sensor, a thermal conductivity sensor,and/or an ionization sensor.

This disclosure also provides kits for reducing the emissions ofexisting vehicles. The kits may comprise the host material storagevessel 260, the clathrate formation system 240, and the exhaust storagevessel 250 disclosed above for the vehicle 300. The clathrate formationsystem 240 may be configured for operable connection to an engine of avehicle, configured to be operably connected to the host materialstorage vessel 260, and configured to combine an exhaust stream from theengine with host material to form carbon dioxide clathrates. The exhauststorage vessel 250 may be configured to store carbon dioxide clathrates.It should be understood that any and all of the disclosure aboveregarding the vehicle 300, other than the disclosure specific to theengine 230, may apply to the kits. Additionally, the kits include theoption that any components disclosed for the vehicle 300 as beingoperably connected to another component may instead be configured foroperable connection.

In some embodiments, the kits are configured to be mounted underneaththe trunk area of a vehicle. In other embodiments, the kits areconfigured to be mounted in the trunk of the vehicle.

The kits may be for any number of conventional vehicles, such as, forexample, a locomotive, a tractor configured for attachment to asemi-trailer, a bus, a car, or a pick-up truck. The kits may be usedwith any number of conventional engines, such as, for example, agasoline engine, a diesel engine, or a natural gas engine.

The kits may comprise a host material storage vessel 260 configured tosupply host material to the clathrate formation system 240, wherein thehost material storage vessel 260 is operably connected to the clathrateformation system 240. The kits may further comprise a transport deviceconfigured to transport host material from the host material storagevessel 260 to the clathrate formation system 240. The host materialstorage vessel 260 may be configured to receive previously unused and/orrecycled host material.

The kits may comprise a filter configured to separate non-carbonproducts from the exhaust stream.

The kits may comprise a catalytic converter configured to convert carbonmonoxide and uncombusted hydrocarbons to carbon dioxide. Alternatively,the kits may be configured to utilize an existing catalytic converter ofa vehicle to convert carbon monoxide and uncombusted hydrocarbons tocarbon dioxide.

The clathrate formation system 240 of the kits may be configured toutilize combustion produced water as at least a portion of the hostmaterial in the formation of carbon dioxide clathrates. In addition tocarbon dioxide clathrates, the clathrate formation system 240 may beconfigured to also form carbon monoxide clathrates and partiallycombusted hydrocarbon clathrates. For example, the clathrate formationsystem 240 may be configured to control the pressure and temperature ofthe exhaust stream and the host material sufficient to form partiallycombusted hydrocarbon clathrates with partially combusted hydrocarbonsand host material, to form carbon monoxide clathrates with carbonmonoxide and host material, and/or to form carbon dioxide clathrateswith carbon dioxide and host material. Likewise, the exhaust storagevessel 250 may also be configured to form carbon monoxide clathrates andpartially combusted hydrocarbon clathrates in addition to carbon dioxideclathrates.

The clathrate formation system 240 of the kits may comprise a coolingsystem configured to cool the exhaust stream. The cooling system maycomprise a heat exchanger configured to transfer heat from the exhauststream to an external heat sink, such as ambient air.

The clathrate formation system 240 of the kits may comprise apressurization system. The pressurization system may comprise acompressor. Examples of a compressor include, but are not limited to, acentrifugal compressor, a mixed-flow compressor, an axial-flowcompressor, a reciprocating compressor, a rotary screw compressor, arotary vane compressor, a scroll compressor, and a diaphragm compressor.

The clathrate formation system 240 of the kits may comprise a formationvessel operably connected to the exhaust storage vessel 250.

The clathrate formation system 240 of the kits may further comprise acarbon dioxide removal system configured to separate carbon dioxide fromthe exhaust stream and deliver the removed carbon dioxide to theformation vessel. The carbon dioxide removal system may comprise aremoval vessel configured to be operably connected to the exhaust streamand the formation vessel.

The removal vessel of the kits may be configured to contact the exhauststream with at least one separation fluid. The separation fluid maycomprise a chemical solvent. The separation fluid may comprise aphysical solvent. Examples of the separation fluid include fluidscomprising an alkanolamine, a monoethanolamine, a diethanolamine, amethyldiethanolamine, a triethanolamine, and/or piperazine. Theseparation fluid may be a liquid. The separation fluid may comprise hostmaterial.

The kits may further comprise a regeneration system configured toseparate carbon dioxide from the separation fluid and operably coupledto the removal vessel. The regeneration system may comprise aregeneration vessel operably coupled to the removal vessel andconfigured to heat the separation fluid. The regeneration vessel may beconfigured to operate on a batch basis. The regeneration vessel may beconfigured to operate on a continuous basis. The regeneration vessel maycomprise a tank. The regeneration vessel may comprise a conduit.

In some embodiments of the kits, the removal vessel is configured tocontact the exhaust stream with an alkali carbonate, such as sodiumcarbonate and/or potassium carbonate. In such embodiments, the vehicle300 may further comprise a regeneration system configured to separatecarbon dioxide from the alkali carbonate and operably coupled to theremoval vessel. The regeneration system may comprise a regenerationvessel operably coupled to the removal vessel and configured to heat thealkali carbonate. The regeneration vessel may be configured to operateon a batch basis or on a continuous basis. The regeneration vessel maycomprise a tank and/or a conduit.

In some embodiments of the kits, the removal vessel comprises a membraneconfigured to separate carbon dioxide from the exhaust stream. Themembrane may comprise a polymer, such as a cellulose acetate polymer, apolyimide polymer, a polyamide polymer, a polycarbonate polymer, apolysulfone polymer, and/or a polyetherimide polymer. The membrane maycomprise flat sheets. The flat sheets may be spiral-wound. The membranemay comprise hollow fibers.

The removal vessel of the kits may be configured to operate on a batchbasis. For example, the removal vessel may comprise a tank. The removalvessel may be configured to operate on a continuous basis. For example,the removal vessel may comprise a conduit.

The clathrate formation system 240 of the kits may be configured tocontrol the rate of formation of the carbon dioxide clathrates byregulating at least one of the temperature and the pressure of exhaustgases within the formation vessel. The formation vessel may furthercomprise insulation configured to maintain an internal temperature ofthe formation vessel. The insulation may comprise at least one materialconfigured to and compatible with maintaining desired temperatureswithin the formation vessel. Examples of such materials include, but arenot limited to, calcium silicate, cellular glass, elastomeric foam,fiberglass, polyisocyanurate, polystyrene, and polyurethane. Theinsulation may comprise at least one vacuum layer and/or multi-layerinsulation. The insulation may releasably surround at least a portion ofan outer surface of the vessel and/or the insulation may be attached toat least a portion of a surface of the vessel, including an outer and/orinner surface.

The kits may further comprise a refrigeration system configured tomaintain an internal temperature of the formation vessel within a setrange. The refrigeration system may also be configured to cool theexhaust stream. The set range may be from about 0 degrees Centigrade toabout 25 degrees Centigrade, including from about 0 degrees Centigradeto about 20 degrees Centigrade, including from about 0 degreesCentigrade to about 15 degrees Centigrade, including from about 0degrees Centigrade to about 10 degrees Centigrade, and including fromabout 4 degrees Centigrade to about 10 degrees Centigrade.

The refrigeration system may comprise a heat pipe configured and locatedto control the temperature of the formation vessel. The refrigerationsystem may also comprise a vapor compression system. The vaporcompression system may utilize a chlorofluorocarbon, achlorofluoroolefin, a hydrochlorofluorocarbon, ahydrochloro-fluoroolefin, a hydrofluoroolefin, a hydrochloroolefin, ahydroolefin, a hydrocarbon, a perfluoroolefin, a perfluorocarbon, aperchloroolefin, a perchlorocarbon, and/or a halon. The refrigerationsystem may comprise a vapor absorption system. The vapor absorptionsystem may utilize water, ammonia, and/or lithium bromide. Therefrigeration system may comprise a gas cycle refrigeration system, suchas one that utilizes air. The refrigeration system may comprise astirling cycle refrigeration system. The stirling cycle refrigerationsystem may utilize helium. The stirling cycle refrigeration system maycomprise a free piston stirling cooler. The refrigeration system maycomprise a thermoelectric refrigeration system.

The clathrate formation system 240 of the kits may be configured togenerate an internal pressure in the formation vessel of about ambientpressure to about 30 bar, an internal pressure of about 10 bar to about30 bar, an internal pressure of about 10 bar to about 15 bar, aninternal pressure of about 15 bar to about 27 bar, or an internalpressure of about 20 bar to about 27 bar. The formation vessel may bedesigned to leak or vent before burst. The formation vessel may furthercomprise a pressure relief device operably connected to the vessel andconfigured to reduce pressure within the vessel. Examples of a pressurerelief device include, but are not limited to, a pressure relief valveand a rupture disc.

The clathrate formation system 240 of the kits may be configured topressurize the exhaust stream in the formation vessel withoutsubstantially increasing back pressure on the exhaust ports of theengine 230. In such embodiments, the clathrate formation system 240 maycomprise a valve operably connected to the formation vessel, wherein thevalve is configured to control introduction of the exhaust stream to theformation vessel. The clathrate formation system 240 may be configuredto sequentially introduce batches of the exhaust stream to the formationvessel. For example, introduction of the exhaust stream batches to theformation vessel may be timed to coincide with the closing of exhaustports of the engine 230.

The clathrate formation system 240 of the kits may further comprise atleast one holding vessel for temporarily storing the exhaust stream at alow pressure prior to introduction of the exhaust stream to theformation vessel for pressurizing. The low pressure may be less than thepressure at which carbon dioxide clathrates are formed in the formationvessel. The low pressure may be substantially equal to what the pressureof the exhaust stream at an exhaust port of the engine 230 would be ifthe clathrate formation system 240 and the exhaust storage vessel 250were not connected to the engine 230. The low pressure may be aboutequal to atmospheric pressure.

The clathrate formation system 240 of the kits may comprise acompressor, wherein an inlet of the compressor is configured to beoperably connected to exhaust ports of the engine 230 and an outlet ofthe compressor is configured to be operably connected to the formationvessel. The compressor may be configured to reduce back pressure onexhaust ports of the engine 230 to be substantially equal to what thepressure at the exhaust ports would be if the clathrate formation system240 and exhaust storage vessel 250 were not connected to the exhauststream. The compressor may be configured to minimize back pressure onthe exhaust ports of the engine 230 while pressurizing the formationvessel. Examples of a compressor include, but are not limited to, acentrifugal compressor, a mixed-flow compressor, an axial-flowcompressor, a reciprocating compressor, a rotary screw compressor, arotary vane compressor, a scroll compressor, and a diaphragm compressor.

The formation vessel of the kits may comprise a chamber configured toform batches of carbon dioxide clathrates and/or the formation vesselmay comprise a conduit operably connected to the exhaust storage vessel250 and configured to continuously form carbon dioxide clathrates.

The clathrate formation system 240 of the kits may comprise a moveablepress integrated with the formation vessel and configured to pressurizethe formation vessel. For example, the moveable press may include, butis not limited to, a hydraulic press or an electromagnetically activatedpress.

The clathrate formation system 240 of the kits may further comprise atemperature monitoring system configured to monitor the internaltemperature of the formation vessel. The temperature monitoring systemmay comprise a thermostat, a thermistor, a thermocouple, and/or aresistive temperature detector.

The clathrate formation system 240 of the kits may further comprise apressure monitoring device operably connected to the formation vesseland configured to monitor an internal pressure of the formation vessel.For example, the pressure monitoring device may comprise apiezoresistive strain gauge, a capacitive sensor, an electromagneticsensor, a piezoelectric sensor, an optical sensor, a potentiometricsensor, a thermal conductivity sensor, and/or an ionization sensor.

The clathrate formation system 240 of the kits may further comprise apressure relief device operably connected to the formation vessel andconfigured to reduce pressure within the formation vessel. Examples of apressure relief device include, but are not limited to, a pressurerelief valve and a rupture disc.

The kits may further comprise a transport device operably connected tothe formation vessel and the exhaust storage vessel and configured totransfer carbon dioxide clathrates from the formation vessel to theexhaust storage vessel. The transport device may be configured totransport the carbon dioxide clathrates as a slurry and/or as a solid,such as solid chunks or pellets.

The transport device may be at least partially located internally withinthe formation vessel. Likewise, the transport device may be at leastpartially external to the formation vessel. Accordingly, the transportdevice may be at least partially integrated into a portion of a surface,including an internal or external surface, of the formation vessel.Additionally, the transport device may be at least partially integratedinto a portion of a surface, including an internal or external surface,of the exhaust storage vessel 250. Likewise, the transport device may beat least partially internal and/or external to the exhaust storagevessel 250.

The transport device may be configured for moving solid carbon dioxideclathrate. The transport device may be configured for moving carbondioxide clathrate slurry. The transport device may be configured to behydraulically, mechanically, and/or electrically actuated.

The transport device may comprise an extruder and/or a pump. When thetransport device comprises a pump, the inlet of the pump may be operablyconnected to the formation vessel and an outlet of the pump may beoperably connected to the exhaust storage vessel 250. Examples of thepump include, but are not limited to, a positive displacement pump, alobe pump, an external gear pump, an internal gear pump, a peristalticpump, a screw pump, a progressive cavity pump, a flexible impeller pump,a rotary vane pump, and a centrifugal pump. The pump may be any pumpcompatible with pumping a carbon dioxide clathrate slurry.

The clathrate formation system 240 of the kits may be integrated withthe exhaust storage vessel 250. The clathrate formation system 240 maybe configured to form carbon dioxide clathrates by regulating at leastone of the temperature and the pressure of carbon dioxide and hostmaterial within the exhaust storage vessel 250 to be compatible withforming carbon dioxide clathrates. For example, the temperature may beregulated to be about 0 degrees Centigrade to about 25 degreesCentigrade, may be regulated to be about 0 degrees Centigrade to about20 degrees Centigrade, may be regulated to be about 0 degrees Centigradeto about 15 degrees Centigrade, may be regulated to be about 0 degreesCentigrade to about 10 degrees Centigrade, or may be regulated to beabout 4 degrees Centigrade to about 10 degrees Centigrade. In anotherexample, the pressure may be regulated to be about 1 bar to about 30bar, the pressure may be regulated to be about 10 bar to about 30 bar,the pressure may be regulated to be about 10 bar to about 15 bar, thepressure may be regulated to be about 15 bar to about 27 bar, or thepressure may be regulated to be about 20 bar to about 27 bar.

Likewise, the exhaust storage vessel 250 of the kits may be configuredto agitate the carbon dioxide and the host material at a temperature anda pressure compatible with forming the carbon dioxide clathrates. Forexample, the exhaust storage vessel 250 may comprise a mixing elementlocated within the exhaust storage vessel 250 and configured to agitatethe carbon dioxide and the host material.

Additionally, the exhaust storage vessel 250 of the kits may comprisehigh-surface-area materials configured for forming carbon dioxideclathrates on the surface thereof. By way of non-limiting example, thehigh-surface-area material may comprise a graphene-based material, anactivated carbon, and/or a metal organic framework, such as a bidentatecarboxylic comprising ligand, a tridentate carboxylic comprising ligand,an azole comprising ligand, or a squaric acid comprising ligand.

The clathrate formation system 240 of the kits may further comprise aheat pipe configured and located to modulate the temperature of theexhaust storage vessel 250.

The clathrate formation system 240 of the kits may be configured toreceive a continuous supply of carbon dioxide or may be configured toperiodically receive a batch of carbon dioxide, while the vehicle 300 isoperating. The clathrate formation system 240 may be configured toreceive a variable supply of the exhaust stream based on the quantity ofexhaust produced by the engine 230.

The exhaust storage vessel 250 of the kits may be configured to receivethe carbon dioxide clathrates as a solid and/or as a slurry.

The exhaust storage vessel 250 of the kits may be configured for removalof stored carbon dioxide from the vehicle 300 when the vehicle 300 isotherwise not in use. The exhaust storage vessel 250 may be configuredto reduce the pressure and/or increase the temperature of the exhauststorage vessel 250 sufficient to dissociate the stored carbon dioxideclathrates into carbon dioxide and host material. For example, theexhaust storage vessel 250 may be configured to sufficiently warm storedcarbon dioxide clathrates so as to liquefy the host material and gasifythe carbon dioxide. The exhaust storage vessel 250 may comprise anoutlet configured for removal of dissociated carbon dioxide. The exhauststorage vessel 250 may also comprise an outlet configured for removal ofdissociated host material.

The kits may further comprise a heating system configured and located toimpart heat energy to the exhaust storage vessel 250. The heating systemmay be located internal or external to the vessel. For example, theheating system may be integrated into or attached to a portion of asurface of the exhaust storage vessel 250, including external orinternal surfaces. The heating system may be independently configured totransfer heat energy from the coolant used to cool the engine 230.Likewise, the heating system may be configured to transfer heat energyfrom heat generated by the engine 230 in any fashion, such as from anexhaust stream generated by the engine 230. For example, the heatingsystem may be configured to divert the exhaust stream from the clathrateformation system 240 and also configured to transfer heat from thediverted exhaust stream to the exhaust storage vessel 250. In thatexample, the heating system may be further configured to divert theexhaust stream from the exhaust storage vessel 250 and vent the exhauststream to atmosphere. Alternatively or in addition thereto, the heatingsystem may utilize solar energy, ambient temperatures, electricresistance heating elements, microwave heating, electromagnetic heating,and/or dielectric heating to impart heat energy.

The kits may further comprise a recycle system configured to transferdissociated host material from the exhaust storage vessel 250 to thehost material storage vessel 260. The recycle system may comprise afilter configured to clean dissociated host material prior to transferof the dissociated host material to the host material storage vessel260. The recycle system may comprise a transfer device configured totransfer the dissociated host material to the host material storagevessel 260.

The exhaust storage vessel 250 of the kits may be configured for removalof solid and/or slurry carbon dioxide clathrates from the exhauststorage vessel 250.

The exhaust storage vessel 250 of the kits may be configured to maintaincarbon dioxide clathrates as a solid and/or slurry until removal ofcarbon dioxide from the vehicle 300 is intended.

The exhaust storage vessel 250 of the kits may be configured to bedetachable and reattachable from the remainder of the vehicle 300. Forexample, the exhaust storage vessel 250 may be configured to beexchanged with a different exhaust storage vessel 250 that has beenemptied of carbon dioxide clathrates.

The kits may further comprise a sensor configured to monitor the amountof carbon dioxide clathrates in the exhaust storage vessel 250. Thesensor may be configured to measure a mass of the carbon dioxideclathrates. The sensor may be configured to measure a vapor pressure ofcarbon dioxide gas present in the exhaust storage vessel 250. The sensormay be configured to determine a concentration of carbon dioxide presentin the exhaust storage vessel 250. The sensor may be configured tomonitor the amount of carbon dioxide removed from the exhaust storagevessel 250.

The kits may alternatively comprise a dissociation vessel operablyconnected to the exhaust storage vessel 250 and configured to receivecarbon dioxide clathrates from the exhaust storage vessel 250. Thedissociation vessel may be configured for removal of stored carbondioxide from the vehicle 300 when the vehicle 300 is otherwise not inuse. The dissociation vessel may be configured to reduce the pressureand/or increase the temperature of the dissociation vessel sufficient todissociate the stored carbon dioxide clathrates into carbon dioxide andhost material.

The kits may further comprise a temperature monitoring system configuredto monitor the internal temperature of the exhaust storage vessel 250.The temperature monitoring system may comprise a thermostat, athermistor, a thermocouple, and/or a resistive temperature detector.

The kits may further comprise a control system configured to monitorboth pressure and temperature of the exhaust storage vessel 250 andconfigured to regulate at least one of pressure and temperature in orderto maintain the carbon dioxide clathrate within a clathrate stabilityrange.

The exhaust storage vessel 250 of the kits may comprise insulation. Theinsulation may comprise at least one material configured to andcompatible with maintaining desired temperatures within each vessel.Examples of such materials include, but are not limited to, calciumsilicate, cellular glass, elastomeric foam, fiberglass,polyisocyanurate, polystyrene, and polyurethane. The insulation maycomprise at least one vacuum layer and/or multi-layer insulation. Theinsulation may releasably surround at least a portion of an outersurface of the vessel and/or the insulation may be attached to at leasta portion of a surface of the vessel, including an outer and/or innersurface.

The exhaust storage vessel 250 of the kits may comprise a refrigerationsystem configured to maintain an internal temperature of about 0 degreesCentigrade to about 25 degrees Centigrade. The exhaust storage vessel250 may be configured to maintain an internal temperature of about 0degrees Centigrade to about 20 degrees Centigrade. The exhaust storagevessel 250 may be configured to maintain an internal temperature ofabout 0 degrees Centigrade to about 15 degrees Centigrade. The exhauststorage vessel 250 may be configured to maintain an internal temperatureof about 0 degrees Centigrade to about 10 degrees Centigrade, includingfrom about 4 degrees Centigrade to about 10 degrees Centigrade.

The refrigeration system may comprise a heat pipe. The refrigerationsystem may also comprise a vapor compression system. The vaporcompression system may utilize a chlorofluorocarbon, achlorofluoroolefin, a hydrochlorofluorocarbon, ahydrochloro-fluoroolefin, a hydrofluoroolefin, a hydrochloroolefin, ahydroolefin, a hydrocarbon, a perfluoroolefin, a perfluorocarbon, aperchloroolefin, a perchlorocarbon, and/or a halon. The refrigerationsystem may comprise a vapor absorption system. The vapor absorptionsystem may utilize water, ammonia, and/or lithium bromide. Therefrigeration system may comprise a gas cycle refrigeration system, suchas one that utilizes air. The refrigeration system may comprise astirling cycle refrigeration system. The stirling cycle refrigerationsystem may utilize helium. The stirling cycle refrigeration system maycomprise a free piston stirling cooler. The refrigeration system maycomprise a thermoelectric refrigeration system.

The formation vessel, if present, and the exhaust storage vessel 250 ofthe kits may each be comprised of structural materials configured to andcompatible with maintaining desired temperatures and pressures withineach respective vessel. The structural material may comprise aluminum,brass, copper, ferretic steel, carbon steel, stainless steel,polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE),vinylidene polyfluoride (PVDF), polyamide (PA), polypropylene (PP),nitrile rubber (NBR), chloroprene (CR), chlorofluorocarbons (FKM),and/or composite materials, including composite materials comprisingcarbon fibers, glass fibers, and/or aramid fibers.

The exhaust storage vessel 250 of the kits may be designed to maintainan internal pressure of about 1 bar to about 30 bar, an internalpressure of about 10 bar to about 30 bar, an internal pressure of about10 bar to about 15 bar, an internal pressure of about 15 bar to about 27bar, an internal pressure of about 20 bar to about 27 bar. The vesselmay be designed to leak or vent before burst. The vessel may furthercomprise a pressure relief device operably connected to the vessel andconfigured to reduce pressure within the vessel. Examples of a pressurerelief device include, but are not limited to, a pressure relief valveand a rupture disc.

The kits may further comprise a pressurizing device operably connectedto the exhaust storage vessel 250 and configured to maintain pressurewithin the exhaust storage vessel 250. Examples of a pressurizing deviceinclude a moveable press integrated with the vessel, wherein themoveable press is configured to maintain pressure within the vessel. Forexample, the moveable press may include, but is not limited to, ahydraulic press or an electromagnetically activated press. In otherexamples, the pressurizing device may comprise a compressor. Examples ofa compressor include, but are not limited to, a centrifugal compressor,a mixed-flow compressor, an axial-flow compressor, a reciprocatingcompressor, a rotary screw compressor, a rotary vane compressor, ascroll compressor, and a diaphragm compressor.

The kits may further comprise a pressure monitoring device operablyconnected to the exhaust storage vessel 250 and configured to monitor aninternal pressure of the exhaust storage vessel 250. The pressuremonitoring device may comprise a piezoresistive strain gauge, acapacitive sensor, an electromagnetic sensor, a piezoelectric sensor, anoptical sensor, a potentiometric sensor, a thermal conductivity sensor,and/or an ionization sensor.

FIGS. 4 and 5 illustrate additional embodiments of a vehicle withreduced emissions. In the embodiments illustrated in FIGS. 4 and 5, thefuel is stored in gas clathrates, similar as in the embodimentsillustrated in FIGS. 1 and 2. Unlike the embodiments illustrated inFIGS. 1 and 2, the gas clathrates do not undergo a dissociation processduring the release of the fuel. Also unlike the embodiments illustratedin FIGS. 1-3, carbon dioxide clathrates are not formed by associatingcarbon dioxide with a liquid host material. Instead, in the embodimentsillustrated in FIGS. 4 and 5, exhaust gas molecules, such as carbondioxide, are exchanged with the fuel molecules, such as methane, withoutdissociating the clathrate structure. Without wishing to be bound bytheory, it is believed that at appropriate temperatures and pressures,exhaust gas molecules, such as carbon dioxide, are thermodynamicallyfavored over fuel molecules, such as methane, in the clathratestructure. Therefore, exhaust gas molecules, such as carbon dioxide, maydiffuse into the gas clathrate structure and liberate fuel molecules,such as methane, without the host material changing phase to liquid.Therefore, although the exchange process may result in the formation ofcarbon dioxide clathrates, the carbon dioxide clathrates are not formedfrom liquid host material.

FIG. 4 illustrates a vehicle 400 with gas clathrates and carbon dioxideclathrates stored in the same vessel, clathrate storage vessel 310.Accordingly, the disclosure regarding the clathrate storage vessel 110of the vehicle 200 may be applicable to the clathrate storage vessel 310and vice versa. FIG. 5 illustrates a vehicle 500 comprising a fuelstorage vessel 410 and an exhaust storage vessel 450 for separatelystoring the gas clathrates and the carbon dioxide clathrates.Accordingly, the disclosure regarding the fuel storage vessel 10 and theexhaust storage vessel 50 of the vehicle 100 may apply to the fuelstorage vessel 410 and the exhaust storage vessel 450 of the vehicle 500and vice versa. For example, the disclosure above regarding the chemicalcomposition of the gas clathrates, the at least one gas, and the hostmaterial of the vehicle 100 and the vehicle 200 also applies to the samefor the vehicle 400 and the vehicle 500.

The vehicle 400 comprises a clathrate storage vessel 310 configured tostore gas clathrates at a first temperature and a first pressure. Thevehicle 400 may further comprise an engine 330 operably connected to theclathrate storage vessel 310 and configured to receive discharged atleast one gas from the clathrate storage vessel 310. The vehicle 400 mayfurther comprise an exhaust delivery system operably connected to theengine 330 and configured to introduce carbon dioxide from an exhauststream from the engine 330 into the clathrate storage vessel 310 at atemperature and pressure substantially the same as the first temperatureand pressure. The clathrate storage vessel 310 may be configured todischarge the at least one gas and store carbon dioxide clathrates.

The clathrate storage vessel 310 may be configured to control the rateof exchange of carbon dioxide for the at least one gas by regulating atleast one of the temperature and the pressure of the clathrate storagevessel 310.

The clathrate storage vessel 310 may be configured to spontaneouslyexchange carbon dioxide for the at least one gas within the gasclathrates without substantially melting any host material of the gasclathrates, wherein gas clathrates are converted to carbon dioxideclathrates and the at least one gas is released.

The clathrate storage vessel 310 may be configured to receive the atleast one gas and the host material and configured to form the gasclathrates within the clathrate storage vessel 310, similar as disclosedabove for the clathrate storage vessel 110. For example, the clathratestorage vessel 310 may be configured to agitate, such as with a mixingelement, the at least one gas and the host material at a temperature anda pressure compatible with forming the gas clathrates from the at leastone gas and the host material. The clathrate storage vessel 310 maycomprise high-surface-area materials configured for forming clathrateson the surface of the materials. The high-surface-area materials may beconfigured for forming gas clathrates and carbon dioxide clathrates,where formation depends upon the conditions within the clathrate storagevessel 310 and the gases present. The high-surface-area materials may bethe same as disclosed above for the fuel storage vessel 10 and theclathrate storage vessel 110.

The clathrate storage vessel 310 may be configured to be detachable andreattachable from the remainder of the vehicle 400. For example, theclathrate storage vessel 310 may be configured to be exchanged with adifferent clathrate storage vessel 310 that has had carbon dioxideclathrates removed and been pre-filled with gas clathrates.

The clathrate storage vessel 310 may be configured to receive the gasclathrates as a slurry or a solid. The clathrate storage vessel 310 maybe configured to maintain the gas clathrates as a slurry or a solid,such as solid pellets or chunks.

The clathrate storage vessel 310 may comprise insulation. The disclosureregarding insulation options for the fuel storage vessel 10 and theclathrate storage vessel 110 also apply to the insulation options forthe clathrate storage vessel 310.

Likewise, the clathrate storage vessel 310 may comprise a refrigerationsystem configured to maintain an internal temperature of the clathratestorage vessel 310 within a set range. The disclosure regardingrefrigeration system options and set range options for the fuel storagevessel 10 and the clathrate storage vessel 110 also applies torefrigeration system options and set range options for the clathratestorage vessel 310. Similarly, the structural material options disclosedfor the fuel storage vessel 10 and the clathrate storage vessel 110 alsoapply to the structural material options for the clathrate storagevessel 310.

The vehicle 400 may further comprise a sensor configured to monitor theamount of gas clathrates and/or carbon dioxide clathrates in theclathrate storage vessel 310. The disclosure regarding sensor optionsfor the vehicle 100 and the vehicle 200 also apply to the sensor optionsfor the vehicle 400.

The clathrate storage vessel 310 may be designed to maintain an internalpressure of about 1 bar to about 30 bar, including the narrower rangesdisclosed for the fuel storage vessel 10 and the clathrate storagevessel 110. The clathrate storage vessel 310 may be designed to leak orvent before burst. The clathrate storage vessel 310 may be operablyconnected to a pressure monitoring device, a pressurizing device, and/ora pressure relief device. The disclosure regarding a pressure monitoringdevice, a pressurizing device, and/or a pressure relief device optionsfor the vehicle 100 and the vehicle 200 also applies to pressuremonitoring device, pressurizing device, and/or pressure relief deviceoptions for the vehicle 400.

The vehicle 400 may further comprise a heating system configured andlocated to impart heat energy to the clathrate storage vessel 310. Thevehicle 400 may further comprise a temperature monitoring systemconfigured to monitor the internal temperature of the clathrate storagevessel 310. The vehicle 400 may further comprise an emergency coolingsystem configured to rapidly cool the clathrate storage vessel 310. Thevehicle 400 may further comprise a control system configured to monitorboth pressure and temperature and to regulate at least one of thepressure and temperature in order to maintain clathrate within aclathrate stability range. The disclosure regarding a heating system, atemperature monitoring system, an emergency cooling system, and acontrol system for the vehicle 100 and the vehicle 200 and theirrespective vessels also applies to the same for the vehicle 400 and theclathrate storage vessel 310.

The clathrate storage vessel 310 may comprise a conduit configured as aplug flow reactor and/or a chamber configured as a batch reactor.

The clathrate storage vessel 310 may comprise a gas outlet configuredfor removing at least one gas from the clathrate storage vessel 310. Theclathrate storage vessel 310 may further comprise a control valveoperably connected to the gas outlet and to the engine 330, wherein thecontrol valve is configured to control release of stored at least onegas from the clathrate storage vessel 310. The clathrate storage vessel310 may further comprise a metering system configured to controlintroduction of stored at least one gas to the engine 330. The meteringsystem may comprise a gas flow meter configured to measure the flow rateof the stored at least one gas released from the clathrate storagevessel 310. The vehicle 400 may further comprise a transport deviceconfigured to transport the at least one gas from the clathrate storagevessel 310 to the engine 330, wherein the transport device is operablyconnected to the clathrate storage vessel 310 and to the engine 330. Thetransport device may be configured to control the transport of the atleast one gas based on fuel requirements of the engine 330. Thetransport device may comprise a compressor, including, but not limitedto, a compressor exemplified in the disclosure regarding the separationsystem 20 and/or the separation system 120.

The vehicle 400 may further comprise a gas storage vessel configured tostore the at least one gas removed from the clathrate storage vessel310, wherein the gas storage vessel is operably connected to theclathrate storage vessel 310 and is operably connected to the engine330. In such embodiments, the vehicle 400 may further comprise a controlvalve operably connected to the gas storage vessel and to the engine330, wherein the control valve is configured to control release ofstored at least one gas from the gas storage vessel. The vehicle 400 mayfurther comprise a metering system configured to control introduction ofstored at least one gas to the engine 330. The metering system maycomprise a gas flow meter configured to measure the flow rate of thestored at least one gas released from the gas storage vessel. Thevehicle 400 may further comprise a transport device configured totransport the at least one gas from the gas storage vessel to the engine330, wherein the transport device is operably connected to the gasstorage vessel and to the engine 330. The transport device may beconfigured to control the transport of the at least one gas based onfuel requirements of the engine 330. The transport device may comprise acompressor, including, but not limited to, a compressor exemplified inthe disclosure regarding the separation system 20 and/or the separationsystem 120.

The vehicle 400 may further comprise a control valve operably connectedto the clathrate storage vessel 310 and to the gas storage vessel,wherein the control valve is configured to control release of stored atleast one gas from the clathrate storage vessel 310. The vehicle 400 mayfurther comprise a metering system configured to control introduction ofstored at least one gas from the clathrate storage vessel 310 to the gasstorage vessel. The metering system may comprise a gas flow meterconfigured to measure the flow rate of the stored at least one gasreleased from the clathrate storage vessel 310. The vehicle 400 mayfurther comprise a transport device configured to transport the at leastone gas from the clathrate storage vessel 310 to the gas storage vessel,wherein the transport device is operably connected to the clathratestorage vessel 310 and to the gas storage vessel. The transport devicemay be configured to control the transport of the at least one gas basedon fuel requirements of the engine 330. The transport device maycomprise a compressor, including, but not limited to, a compressorexemplified in the disclosure regarding the separation system 20 and/orthe separation system 120.

The vehicle 400 may further comprise a cooling device configured toreduce the temperature of the at least one gas prior to introduction ofthe at least one gas to the engine 330. The cooling device may comprisea heat exchanger. The heat exchanger may be configured to be cooled byambient air. The heat exchanger may be configured to be cooled by acoolant also used to cool the engine 330. The cooling device maycomprise a refrigerated coil configured to cool the at least one gas.

The vehicle 400 may comprise a moisture-removal system configured toremove water from the at least one gas prior to introduction of the atleast one gas to the engine 330. The moisture-removal system maycomprise, by way of non-limiting example, a dehumidifier, a dryer, or amolecular sieve column.

In some embodiments of the vehicle 400 substantially all of the carbondioxide in the exhaust stream is exchanged for the at least one gas.Therefore, substantially all of the carbon dioxide is captured in carbondioxide clathrates.

In some embodiments of the vehicle 400 the exhaust stream furthercomprises nitrogen. The clathrate storage vessel 310 may be configuredto exchange nitrogen for at least one gas within the gas clathrateswithout substantially melting any host material of the gas clathrates,wherein gas clathrates are converted to nitrogen clathrates and the atleast one gas is released. The clathrate storage vessel 310 may beconfigured to spontaneously exchange nitrogen for at least one gaswithin the gas clathrates.

The vehicle 400 may comprise a filter configured to separate non-carbonproducts from the exhaust stream.

The vehicle 400 may comprise a catalytic converter configured to convertcarbon monoxide and uncombusted hydrocarbons to carbon dioxide. Examplesof partially combusted hydrocarbons include hydrocarbons with one, two,or three carbons.

The clathrate storage vessel 310 may also be configured to exchangecarbon monoxide from the exhaust stream for at least one gas within thegas clathrates. Likewise, the clathrate storage vessel 310 may beconfigured to exchange partially combusted hydrocarbon from the exhauststream for at least one gas within the gas clathrates.

The exhaust delivery system may comprise a cooling system configured tocool the exhaust stream. The cooling system may comprise a heatexchanger configured to transfer heat from the exhaust stream to anexternal heat sink, such as ambient air.

The exhaust delivery system may comprise a pressurization system. Thepressurization system may comprise a compressor. Examples of acompressor include, but are not limited to, a centrifugal compressor, amixed-flow compressor, an axial-flow compressor, a reciprocatingcompressor, a rotary screw compressor, a rotary vane compressor, ascroll compressor, and a diaphragm compressor.

The clathrate storage vessel 310 may be configured to receive acontinuous supply of carbon dioxide while the vehicle 400 is operating.The clathrate storage vessel 310 may be configured to periodicallyreceive a batch of carbon dioxide while the vehicle 400 is operating.The clathrate storage vessel 310 may be configured to receive a variablesupply of the exhaust stream based on the quantity of exhaust producedby the engine 330. The exhaust stream including the carbon dioxide maybe introduced to the clathrate storage vessel 310 with the carbondioxide present in the exhaust stream. The carbon dioxide may be removedfrom the exhaust stream prior to introduction of the carbon dioxide tothe clathrate storage vessel 310.

The vehicle 400 may further comprise a carbon dioxide removal systemconfigured to separate carbon dioxide from the exhaust stream anddeliver the removed carbon dioxide to the clathrate storage vessel 310.The carbon dioxide removal system may comprise a removal vessel operablyconnected to the exhaust stream and the clathrate storage vessel 310.

The removal vessel may be configured to contact the exhaust stream withat least one separation fluid. The separation fluid may comprise achemical solvent. The separation fluid may comprise a physical solvent.Examples of the separation fluid include fluids comprising analkanolamine, a monoethanolamine, a diethanolamine, amethyldiethanolamine, a triethanolamine, and/or piperazine. Theseparation fluid may be a liquid. The separation fluid may comprise hostmaterial.

The vehicle 400 may further comprise a regeneration system configured toseparate carbon dioxide from the separation fluid and operably coupledto the removal vessel. The regeneration system may comprise aregeneration vessel operably coupled to the removal vessel andconfigured to heat the separation fluid. The regeneration vessel may beconfigured to operate on a batch basis. The regeneration vessel may beconfigured to operate on a continuous basis. The regeneration vessel maycomprise a tank. The regeneration vessel may comprise a conduit.

In some embodiments, the removal vessel is configured to contact theexhaust stream with an alkali carbonate, such as sodium carbonate and/orpotassium carbonate. In such embodiments, the vehicle 400 may furthercomprise a regeneration system configured to separate carbon dioxidefrom the alkali carbonate and operably coupled to the removal vessel.The regeneration system may comprise a regeneration vessel operablycoupled to the removal vessel and configured to heat the alkalicarbonate. The regeneration vessel may be configured to operate on abatch basis or on a continuous basis. The regeneration vessel maycomprise a tank and/or a conduit.

In some embodiments, the removal vessel comprises a membrane configuredto separate carbon dioxide from the exhaust stream. The membrane maycomprise a polymer, such as a cellulose acetate polymer, a polyimidepolymer, a polyamide polymer, a polycarbonate polymer, a polysulfonepolymer, and/or a polyetherimide polymer. The membrane may comprise flatsheets. The flat sheets may be spiral-wound. The membrane may comprisehollow fibers.

The removal vessel may be configured to operate on a batch basis. Forexample, the removal vessel may comprise a tank. The removal vessel maybe configured to operate on a continuous basis. For example, the removalvessel may comprise a conduit.

The clathrate storage vessel 310 may be configured for removal of storedcarbon dioxide from the vehicle 400 when the vehicle 400 is otherwisenot in use. The clathrate storage vessel 310 may be configured to reducethe pressure and/or increase the temperature of the clathrate storagevessel 310 sufficient to dissociate the stored carbon dioxide clathratesinto carbon dioxide and host material. For example, the clathratestorage vessel 310 may be configured to sufficiently warm stored carbondioxide clathrates so as to liquefy the host material and gasify thecarbon dioxide. The clathrate storage vessel 310 may comprise an outletconfigured for removal of dissociated carbon dioxide. The clathratestorage vessel 310 may also comprise an outlet configured for removal ofdissociated host material. The vehicle 400 may further comprise arecycle system configured to reuse host material dissociated from thecarbon dioxide clathrates. For example, the host material may be reusedin the formation of gas clathrates during refueling of the clathratestorage vessel 310.

The clathrate storage vessel 310 may be configured for removal of solidand/or slurry carbon dioxide clathrates from the clathrate storagevessel 310.

The clathrate storage vessel 310 may be configured to maintain carbondioxide clathrates as a solid and/or slurry until removal of carbondioxide from the vehicle 400 is intended.

The vehicle 400 may comprise a dissociation vessel operably connected tothe clathrate storage vessel 310 and configured to receive carbondioxide clathrates from the clathrate storage vessel 310. Thedissociation vessel may be configured for removal of stored carbondioxide from the vehicle 400 when the vehicle 400 is otherwise not inuse. The dissociation vessel may be configured to reduce the pressureand/or increase the temperature of the dissociation vessel sufficient todissociate the stored carbon dioxide clathrates into carbon dioxide andhost material.

The vehicle 500 comprises a fuel storage vessel 410 configured to storegas clathrates and an exchange vessel 470 operably connected to the fuelstorage vessel 410 and configured to receive the gas clathrates. Theexchange vessel 470 may be configured to maintain the gas clathrates ata first temperature and a first pressure and may be configured toexchange carbon dioxide for at least one gas within the gas clathrates.The exchange vessel 470 may be configured to discharge the at least onegas and also discharge the carbon dioxide clathrates. The vehicle 500may further comprise an engine 430 operably connected to the exchangevessel 470 and configured to receive discharged gas from the exchangevessel 470.

The vehicle 500 may further comprise an exhaust delivery system operablyconnected to the engine 430 and configured to introduce carbon dioxidefrom an exhaust stream from the engine 430 into the exchange vessel 470at a temperature and pressure substantially the same as the firsttemperature and pressure. The vehicle 500 may further comprise anexhaust storage vessel 450 configured to receive the carbon dioxideclathrates from the exchange vessel 470.

The carbon dioxide may be removed from the exhaust stream prior tointroduction of the carbon dioxide to the exchange vessel 470. Theexhaust stream including the carbon dioxide may be introduced to theexchange vessel 470 with the carbon dioxide present in the exhauststream.

The exchange vessel 470 may be configured to control the rate ofexchange of carbon dioxide for the at least one gas by regulating atleast one of the temperature and the pressure of the exchange vessel470.

The exchange vessel 470 may be configured to spontaneously exchangecarbon dioxide for the at least one gas within the gas clathrateswithout substantially melting any host material of the gas clathrates,wherein gas clathrates are converted to carbon dioxide clathrates andthe at least one gas is released.

The fuel storage vessel 410 may be configured to receive the at leastone gas and the host material and configured to form the gas clathrateswithin the fuel storage vessel 410, similar as disclosed above for theclathrate storage vessel 110. For example, the fuel storage vessel 410may be configured to agitate, such as with a mixing element, the atleast one gas and the host material at a temperature and a pressurecompatible with forming the gas clathrates from the at least one gas andthe host material. The fuel storage vessel 410 may comprisehigh-surface-area materials configured for forming clathrates on thesurface of the materials. The high-surface-area materials may beconfigured for forming gas clathrates and carbon dioxide clathrates,where formation depends upon the conditions within the fuel storagevessel 410 and the gases present. The high-surface-area materials may bethe same as disclosed above for the fuel storage vessel 10 and theclathrate storage vessel 110.

The fuel storage vessel 410 may be configured to be detachable andreattachable from the remainder of the vehicle 500. For example, thefuel storage vessel 410 may be configured to be exchanged with adifferent fuel storage vessel 410 that has been pre-filled with gasclathrates.

The fuel storage vessel 410 may be configured to receive the gasclathrates as a slurry or a solid. The fuel storage vessel 410 may beconfigured to maintain the gas clathrates as a slurry or a solid, suchas solid pellets or chunks.

The fuel storage vessel 410 may comprise insulation. The disclosureregarding insulation options for the fuel storage vessel 10 and theclathrate storage vessel 110 also apply to the insulation options forthe fuel storage vessel 410.

Likewise, the fuel storage vessel 410 may comprise a refrigerationsystem configured to maintain an internal temperature of the fuelstorage vessel 410 within a set range. The disclosure regardingrefrigeration system options and set range options for the fuel storagevessel 10 and the clathrate storage vessel 110 also applies torefrigeration system options and set range options for the fuel storagevessel 410. Similarly, the structural material options disclosed for thefuel storage vessel 10 and the clathrate storage vessel 110 also applyto the structural material options for the fuel storage vessel 410.

The vehicle 400 may further comprise a sensor configured to monitor theamount of gas clathrates in the fuel storage vessel 410. The disclosureregarding sensor options for the vehicle 100 and the vehicle 200 alsoapply to the sensor options for the vehicle 400.

The fuel storage vessel 410 may be designed to maintain an internalpressure of about 1 bar to about 30 bar, including the narrower rangesdisclosed for the fuel storage vessel 10 and the clathrate storagevessel 110. The fuel storage vessel 410 may be designed to leak or ventbefore burst. The fuel storage vessel 410 may be operably connected to apressure monitoring device, a pressurizing device, and/or a pressurerelief device. The disclosure regarding a pressure monitoring device, apressurizing device, and/or a pressure relief device options for thevehicle 100 and the vehicle 200 also applies to pressure monitoringdevice, pressurizing device, and/or pressure relief device options forthe vehicle 500.

The vehicle 500 may further comprise a heating system configured andlocated to impart heat energy to the fuel storage vessel 410. Thevehicle 500 may further comprise a temperature monitoring systemconfigured to monitor the internal temperature of the fuel storagevessel 410. The vehicle 500 may further comprise an emergency coolingsystem configured to rapidly cool the fuel storage vessel 410. Thevehicle 500 may further comprise a control system configured to monitorboth pressure and temperature and to regulate at least one of thepressure and temperature in order to maintain the gas clathrate within aclathrate stability range. The disclosure regarding a heating system, atemperature monitoring system, an emergency cooling system, and acontrol system for the vehicle 100 and the vehicle 200 and theirrespective vessels also applies to the same for the vehicle 500 and thefuel storage vessel 410.

The vehicle 500 may further comprise a valve operably connected betweenthe exchange vessel 470 and the fuel storage vessel 410. The valve maycomprise a passive valve, such as, for example, a ball check valve, adiaphragm check valve, a swing check valve, a stop check valve, or alift check valve. The valve may comprise an active valve, such as, forexample, a globe valve, a butterfly valve, a gate valve, or a ballvalve.

The vehicle 500 may further comprise a transport device operablyconnected to the fuel storage vessel 410 and operably connected to theexchange vessel 470 and configured to transfer gas clathrates from thefuel storage vessel 410 to the exchange vessel 470. The transport devicemay be configured to transport the gas clathrates as a slurry and/or asa solid, such as solid chunks or pellets.

The transport device may be at least partially located internally withinthe fuel storage vessel 410. Likewise, the transport device may be atleast partially external to the fuel storage vessel 410. Accordingly,the transport device may be at least partially integrated into a portionof a surface, including an internal or external surface, of the fuelstorage vessel 410. Additionally, the transport device may be at leastpartially integrated into a portion of a surface, including an internalor external surface, of the exchange vessel 470. Likewise, the transportdevice may be at least partially internal and/or external to theseparation vessel.

The transport device may be configured for moving solid gas clathrate.The transport device may be configured for moving gas clathrate slurry.The transport device may be configured to be hydraulically,mechanically, and/or electrically actuated.

The transport device may comprise an extruder and/or a pump. When thetransport device comprises a pump, the inlet of the pump may be operablyconnected to the fuel storage vessel 410 and an outlet of the pump maybe operably connected to the exchange vessel 470. Examples of the pumpinclude, but are not limited to, a positive displacement pump, a lobepump, an external gear pump, an internal gear pump, a peristaltic pump,a screw pump, a progressive cavity pump, a flexible impeller pump, arotary vane pump, and a centrifugal pump. The pump may be any pumpcompatible with pumping a gas clathrate slurry.

The exchange vessel 470 may comprise insulation configured to maintainan internal temperature of the exchange vessel 470. The insulation maycomprise at least one material configured to and compatible withmaintaining refrigerated temperatures within the separation vessel.Examples of such materials include, but are not limited to, calciumsilicate, cellular glass, elastomeric foam, fiberglass,polyisocyanurate, polystyrene, and polyurethane. The insulation maycomprise at least one vacuum layer and/or multi-layer insulation. Theinsulation may be attached to at least a portion of a surface of thevessel, including an outer and/or inner surface.

The vehicle 500 may further comprise a refrigeration system configuredto maintain an internal temperature of the exchange vessel 470 within aset range. The set range may be from about 0 degrees Centigrade to about25 degrees Centigrade, including from about 0 degrees Centigrade toabout 20 degrees Centigrade, including from about 0 degrees Centigradeto about 15 degrees Centigrade, including from about 0 degreesCentigrade to about 10 degrees Centigrade, and including from about 4degrees Centigrade to about 10 degrees Centigrade.

The refrigeration system may comprise a heat pipe configured and locatedto control the temperature of the exchange vessel 470. The refrigerationsystem may also comprise a vapor compression system. The vaporcompression system may utilize a chlorofluorocarbon, achlorofluoroolefin, a hydrochlorofluorocarbon, ahydrochloro-fluoroolefin, a hydrofluoroolefin, a hydrochloroolefin, ahydroolefin, a hydrocarbon, a perfluoroolefin, a perfluorocarbon, aperchloroolefin, a perchlorocarbon, and/or a halon. The refrigerationsystem may comprise a vapor absorption system. The vapor absorptionsystem may utilize water, ammonia, and/or lithium bromide. Therefrigeration system may comprise a gas cycle refrigeration system, suchas one that utilizes air. The refrigeration system may comprise astirling cycle refrigeration system. The stirling cycle refrigerationsystem may utilize helium. The stirling cycle refrigeration system maycomprise a free piston stirling cooler. The refrigeration system maycomprise a thermoelectric refrigeration system.

The exchange vessel 470 may further comprise a heat pipe configured andlocated to control the temperature of the exchange vessel 470 separatefrom a refrigeration system.

The vehicle 500 may comprise a heating system configured and located toimpart heat energy to the exchange vessel 470. The heating system may belocated internal or external to the vessel. For example, the heatingsystem may be integrated into or attached to a portion of a surface ofthe separation vessel, including external or internal surfaces. Theheating system may be independently configured to transfer heat energyfrom the coolant used to cool the engine 430. Likewise, the heatingsystem may be configured to transfer heat energy from heat generated bythe engine 430 in any fashion, such as from an exhaust stream generatedby the engine 430. Alternatively or in addition thereto, the heatingsystem may utilize solar energy, ambient temperatures, electricresistance heating elements, microwave heating, electromagnetic heating,and/or dielectric heating to impart heat energy.

The exchange vessel 470 may be designed to leak or vent before burst.

The exchange vessel 470 may further comprise a pressure monitoringdevice operably connected to the exchange vessel 470 and configured tomonitor an internal pressure of the exchange vessel 470. The pressuremonitoring device may independently comprise a piezoresistive straingauge, a capacitive sensor, an electromagnetic sensor, a piezoelectricsensor, an optical sensor, a potentiometric sensor, a thermalconductivity sensor, and/or an ionization sensor.

The exchange vessel 470 may further comprise a pressure relief deviceoperably connected to the exchange vessel 470 and configured to reducepressure within the exchange vessel 470. Examples of a pressure reliefdevice include, but are not limited to, a pressure relief valve and arupture disc.

The exchange vessel 470 may further comprise a pressurizing deviceoperably connected to the separation vessel and configured to maintainpressure within the separation vessel. Examples of a pressurizing deviceinclude a moveable press integrated with the vessel, wherein themoveable press is configured to maintain pressure within the vessel. Forexample, the moveable press may include, but is not limited to, ahydraulic press or an electromagnetically activated press. In otherexamples, the pressurizing device may comprise a compressor. Examples ofa compressor include, but are not limited to, a centrifugal compressor,a mixed-flow compressor, an axial-flow compressor, a reciprocatingcompressor, a rotary screw compressor, a rotary vane compressor, ascroll compressor, and a diaphragm compressor.

The exchange vessel 470 may further comprise a temperature monitoringsystem configured to monitor the internal temperature of the separationvessel. The temperature monitoring system may comprise a thermostat, athermistor, a thermocouple, and/or a resistive temperature detector.

The vehicle 500 may further comprise an emergency cooling systemconfigured to rapidly cool the separation vessel.

The vehicle 500 may further comprise a control system configured tomonitor both pressure and temperature of the exchange vessel 470 andconfigured to regulate at least one of pressure and temperature in orderto maintain the gas clathrate and carbon dioxide clathrate within aclathrate stability range.

The exchange vessel 470 may comprise a conduit configured as a plug flowreactor and/or a chamber configured as a batch reactor.

The exchange vessel 470 may comprise a gas outlet configured forremoving at least one gas from the exchange vessel 470. The exchangevessel 470 may further comprise a control valve operably connected tothe gas outlet and to the engine 430, wherein the control valve isconfigured to control release of stored at least one gas from theexchange vessel 470. The exchange vessel 470 may further comprise ametering system configured to control introduction of stored at leastone gas to the engine 430. The metering system may comprise a gas flowmeter configured to measure the flow rate of the stored at least one gasreleased from the exchange vessel 470. The vehicle 500 may furthercomprise a transport device configured to transport the at least one gasfrom the exchange vessel 470 to the engine 430, wherein the transportdevice is operably connected to the exchange vessel 470 and to theengine 430. The transport device may be configured to control thetransport of the at least one gas based on fuel requirements of theengine 430. The transport device may comprise a compressor, including,but not limited to, a compressor exemplified in the disclosure regardingthe separation system 20 and/or the separation system 120.

The vehicle 500 may further comprise a gas storage vessel configured tostore the at least one gas removed from the exchange vessel 470, whereinthe gas storage vessel is operably connected to the exchange vessel 470and is operably connected to the engine 430. In such embodiments, thevehicle 500 may further comprise a control valve operably connected tothe gas storage vessel and to the engine 430, wherein the control valveis configured to control release of stored at least one gas from the gasstorage vessel. The vehicle 500 may further comprise a metering systemconfigured to control introduction of stored at least one gas to theengine 430. The metering system may comprise a gas flow meter configuredto measure the flow rate of the stored at least one gas released fromthe gas storage vessel. The vehicle 500 may further comprise a transportdevice configured to transport the at least one gas from the gas storagevessel to the engine 430, wherein the transport device is operablyconnected to the gas storage vessel and to the engine 430. The transportdevice may be configured to control the transport of the at least onegas based on fuel requirements of the engine 430. The transport devicemay comprise a compressor, including, but not limited to, a compressorexemplified in the disclosure regarding the separation system 20 and/orthe separation system 120.

The vehicle 500 may further comprise a control valve operably connectedto the exchange vessel 470 and to the gas storage vessel, wherein thecontrol valve is configured to control release of stored at least onegas from the exchange vessel 470. The vehicle 500 may further comprise ametering system configured to control introduction of stored at leastone gas from the exchange vessel 470 to the gas storage vessel. Themetering system may comprise a gas flow meter configured to measure theflow rate of the stored at least one gas released from the exchangevessel 470. The vehicle 500 may further comprise a transport deviceconfigured to transport the at least one gas from the exchange vessel470 to the gas storage vessel, wherein the transport device is operablyconnected to the exchange vessel 470 and to the gas storage vessel. Thetransport device may be configured to control the transport of the atleast one gas based on fuel requirements of the engine 430. Thetransport device may comprise a compressor, including, but not limitedto, a compressor exemplified in the disclosure regarding the separationsystem 20 and/or the separation system 120.

The vehicle 500 may further comprise a cooling device configured toreduce the temperature of the at least one gas prior to introduction ofthe at least one gas to the engine 430. The cooling device may comprisea heat exchanger. The heat exchanger may be configured to be cooled byambient air. The heat exchanger may be configured to be cooled by acoolant also used to cool the engine 430. The cooling device maycomprise a refrigerated coil configured to cool the at least one gas.

The vehicle 500 may comprise a moisture-removal system configured toremove water from the at least one gas prior to introduction of the atleast one gas to the engine 430. The moisture-removal system maycomprise, by way of non-limiting example, a dehumidifier, a dryer, or amolecular sieve column.

The exchange vessel 470 may be configured to receive a continuous supplyof gas clathrates while the vehicle 500 is operating. The exchangevessel 470 may be configured to periodically receive a batch of gasclathrates while the vehicle 500 is operating. The exchange vessel maybe configured to receive a variable supply of gas clathrates based onfuel requirements of the engine 430.

In some embodiments of the vehicle 500 substantially all of the carbondioxide in the exhaust stream is exchanged for the at least one gas.Therefore, substantially all of the carbon dioxide is captured in carbondioxide clathrates.

In some embodiments of the vehicle 500 the exhaust stream furthercomprises nitrogen. The exchange vessel 470 may be configured toexchange nitrogen for at least one gas within the gas clathrates withoutsubstantially melting any host material of the gas clathrates, whereingas clathrates are converted to nitrogen clathrates and the at least onegas is released. The exchange vessel 470 may be configured tospontaneously exchange nitrogen for at least one gas within the gasclathrates. The exhaust storage vessel 450 may be configured to storethe nitrogen clathrates.

The vehicle 500 may comprise a filter configured to separate non-carbonproducts from the exhaust stream.

The vehicle 500 may comprise a catalytic converter configured to convertcarbon monoxide and uncombusted hydrocarbons to carbon dioxide. Examplesof partially combusted hydrocarbons include hydrocarbons with one, two,or three carbons.

The exchange vessel 470 may also be configured to exchange carbonmonoxide from the exhaust stream for at least one gas within the gasclathrates. Likewise, the exchange vessel 470 may be configured toexchange partially combusted hydrocarbon from the exhaust stream for atleast one gas within the gas clathrates.

The vehicle 500 may further comprise a carbon dioxide removal systemconfigured to separate carbon dioxide from the exhaust stream anddeliver the removed carbon dioxide to the exchange vessel 470. Thecarbon dioxide removal system may comprise a removal vessel operablyconnected to the exhaust stream and the exchange vessel 470.

The removal vessel may be configured to contact the exhaust stream withat least one separation fluid. The separation fluid may comprise achemical solvent. The separation fluid may comprise a physical solvent.Examples of the separation fluid include fluids comprising analkanolamine, a monoethanolamine, a diethanolamine, amethyldiethanolamine, a triethanolamine, and/or piperazine. Theseparation fluid may be a liquid. The separation fluid may comprise hostmaterial.

The vehicle 500 may further comprise a regeneration system configured toseparate carbon dioxide from the separation fluid and operably coupledto the removal vessel. The regeneration system may comprise aregeneration vessel operably coupled to the removal vessel andconfigured to heat the separation fluid. The regeneration vessel may beconfigured to operate on a batch basis. The regeneration vessel may beconfigured to operate on a continuous basis. The regeneration vessel maycomprise a tank. The regeneration vessel may comprise a conduit.

In some embodiments, the removal vessel is configured to contact theexhaust stream with an alkali carbonate, such as sodium carbonate and/orpotassium carbonate. In such embodiments, the vehicle 500 may furthercomprise a regeneration system configured to separate carbon dioxidefrom the alkali carbonate and operably coupled to the removal vessel.The regeneration system may comprise a regeneration vessel operablycoupled to the removal vessel and configured to heat the alkalicarbonate. The regeneration vessel may be configured to operate on abatch basis or on a continuous basis. The regeneration vessel maycomprise a tank and/or a conduit.

In some embodiments, the removal vessel comprises a membrane configuredto separate carbon dioxide from the exhaust stream. The membrane maycomprise a polymer, such as a cellulose acetate polymer, a polyimidepolymer, a polyamide polymer, a polycarbonate polymer, a polysulfonepolymer, and/or a polyetherimide polymer. The membrane may comprise flatsheets. The flat sheets may be spiral-wound. The membrane may comprisehollow fibers.

The removal vessel may be configured to operate on a batch basis. Forexample, the removal vessel may comprise a tank. The removal vessel maybe configured to operate on a continuous basis. For example, the removalvessel may comprise a conduit.

The exchange vessel 470 may be configured to receive a continuous supplyof carbon dioxide while the vehicle 500 is operating. The exchangevessel 470 may be configured to periodically receive a batch of carbondioxide while the vehicle 500 is operating. The exchange vessel 470 maybe configured to receive a variable supply of the exhaust stream basedon the quantity of exhaust produced by the engine 430.

The exhaust delivery system may comprise a cooling system configured tocool the exhaust stream. The cooling system may comprise a heatexchanger configured to transfer heat from the exhaust stream to anexternal heat sink, such as ambient air.

The exhaust delivery system may comprise a pressurization system. Thepressurization system may comprise a compressor. Examples of acompressor include, but are not limited to, a centrifugal compressor, amixed-flow compressor, an axial-flow compressor, a reciprocatingcompressor, a rotary screw compressor, a rotary vane compressor, ascroll compressor, and a diaphragm compressor.

The vehicle 500 may further comprise a transport device operablyconnected to the exchange vessel 470 and the exhaust storage vessel 450and configured to transfer carbon dioxide clathrates from the exchangevessel 470 to the exhaust storage vessel 450. The transport device maybe configured to transport the carbon dioxide clathrates as a slurryand/or as a solid, such as solid chunks or pellets.

The transport device may be at least partially located internally withinthe exchange vessel 470. Likewise, the transport device may be at leastpartially external to the exchange vessel 470. Accordingly, thetransport device may be at least partially integrated into a portion ofa surface, including an internal or external surface, of the exchangevessel 470. Additionally, the transport device may be at least partiallyintegrated into a portion of a surface, including an internal orexternal surface, of the exhaust storage vessel 450. Likewise, thetransport device may be at least partially internal and/or external tothe exhaust storage vessel 450.

The transport device may be configured for moving solid carbon dioxideclathrate. The transport device may be configured for moving carbondioxide clathrate slurry. The transport device may be configured to behydraulically, mechanically, and/or electrically actuated.

The transport device may comprise an extruder and/or a pump. When thetransport device comprises a pump, the inlet of the pump may be operablyconnected to the exchange vessel 470 and an outlet of the pump may beoperably connected to the exhaust storage vessel 450. Examples of thepump include, but are not limited to, a positive displacement pump, alobe pump, an external gear pump, an internal gear pump, a peristalticpump, a screw pump, a progressive cavity pump, a flexible impeller pump,a rotary vane pump, and a centrifugal pump. The pump may be any pumpcompatible with pumping a carbon dioxide clathrate slurry.

The exhaust storage vessel 450 may be configured for removal of storedcarbon dioxide from the vehicle 500 when the vehicle 500 is otherwisenot in use. The exhaust storage vessel 450 may be configured to reducethe pressure and/or increase the temperature of the exhaust storagevessel 450 sufficient to dissociate the stored carbon dioxide clathratesinto carbon dioxide and host material. For example, the exhaust storagevessel 450 may be configured to sufficiently warm stored carbon dioxideclathrates so as to liquefy the host material and gasify the carbondioxide. The exhaust storage vessel 450 may comprise an outletconfigured for removal of dissociated carbon dioxide. The exhauststorage vessel 450 may also comprise an outlet configured for removal ofdissociated host material. The vehicle 500 may further comprise arecycle system configured to reuse host material dissociated from thecarbon dioxide clathrates. For example, the host material may be reusedin the formation of gas clathrates in the fuel storage vessel 410.

The vehicle 500 may further comprise a heating system configured andlocated to impart heat energy to the exhaust storage vessel 450. Theheating system may be located internal or external to the vessel. Forexample, the heating system may be integrated into or attached to aportion of a surface of the exhaust storage vessel 450, includingexternal or internal surfaces. The heating system may be independentlyconfigured to transfer heat energy from the coolant used to cool theengine 430. Likewise, the heating system may be configured to transferheat energy from heat generated by the engine 430 in any fashion, suchas from an exhaust stream generated by the engine 430. Alternatively orin addition thereto, the heating system may utilize solar energy,ambient temperatures, electric resistance heating elements, microwaveheating, electromagnetic heating, and/or dielectric heating to impartheat energy.

The exhaust storage vessel 450 may be configured for removal of solidand/or slurry carbon dioxide clathrates from the exhaust storage vessel450.

The exhaust storage vessel 450 may be configured to maintain carbondioxide clathrates as a solid and/or slurry until removal of carbondioxide from the vehicle 500 is intended.

The exhaust storage vessel 450 may be configured to be detachable andreattachable from the remainder of the vehicle 500. For example, theexhaust storage vessel 450 may be configured to be exchanged with adifferent exhaust storage vessel 450 that has been emptied of carbondioxide clathrates.

The vehicle 500 may further comprise a sensor configured to monitor theamount of carbon dioxide clathrates in the exhaust storage vessel 450.The sensor may be configured to measure a mass of the carbon dioxideclathrates. The sensor may be configured to measure a vapor pressure ofcarbon dioxide gas present in the exhaust storage vessel 450. The sensormay be configured to determine a concentration of carbon dioxide presentin the exhaust storage vessel 450. The sensor may be configured tomonitor the amount of carbon dioxide removed from the exhaust storagevessel 450.

The vehicle 500 may alternatively comprise a dissociation vesseloperably connected to the exhaust storage vessel 450 and configured toreceive carbon dioxide clathrates from the exhaust storage vessel 450.The dissociation vessel may be configured for removal of stored carbondioxide from the vehicle 500 when the vehicle 500 is otherwise not inuse. The dissociation vessel may be configured to reduce the pressureand/or increase the temperature of the dissociation vessel sufficient todissociate the stored carbon dioxide clathrates into carbon dioxide andhost material.

The exhaust storage vessel 450 may comprise insulation. The insulationmay comprise at least one material configured to and compatible withmaintaining desired temperatures within each vessel. Examples of suchmaterials include, but are not limited to, calcium silicate, cellularglass, elastomeric foam, fiberglass, polyisocyanurate, polystyrene, andpolyurethane. The insulation may comprise at least one vacuum layerand/or multi-layer insulation. The insulation may releasably surround atleast a portion of an outer surface of the vessel and/or the insulationmay be attached to at least a portion of a surface of the vessel,including an outer and/or inner surface.

The exhaust storage vessel 450 may comprise a refrigeration systemconfigured to maintain an internal temperature of about 0 degreesCentigrade to about 25 degrees Centigrade. The exhaust storage vessel450 may be configured to maintain an internal temperature of about 0degrees Centigrade to about 20 degrees Centigrade. The exhaust storagevessel 450 may be configured to maintain an internal temperature ofabout 0 degrees Centigrade to about 15 degrees Centigrade. The exhauststorage vessel 450 may be configured to maintain an internal temperatureof about 0 degrees Centigrade to about 10 degrees Centigrade, includingfrom about 4 degrees Centigrade to about 10 degrees Centigrade.

The refrigeration system may comprise a heat pipe. The refrigerationsystem may also comprise a vapor compression system. The vaporcompression system may utilize a chlorofluorocarbon, achlorofluoroolefin, a hydrochlorofluorocarbon, ahydrochloro-fluoroolefin, a hydrofluoroolefin, a hydrochloroolefin, ahydroolefin, a hydrocarbon, a perfluoroolefin, a perfluorocarbon, aperchloroolefin, a perchlorocarbon, and/or a halon. The refrigerationsystem may comprise a vapor absorption system. The vapor absorptionsystem may utilize water, ammonia, and/or lithium bromide. Therefrigeration system may comprise a gas cycle refrigeration system, suchas one that utilizes air. The refrigeration system may comprise astirling cycle refrigeration system. The stirling cycle refrigerationsystem may utilize helium. The stirling cycle refrigeration system maycomprise a free piston stirling cooler. The refrigeration system maycomprise a thermoelectric refrigeration system.

The exhaust storage vessel 450 may be comprised of structural materialsconfigured to and compatible with maintaining desired temperatures andpressures within the vessel. The structural material may comprisealuminum, brass, copper, ferretic steel, carbon steel, stainless steel,polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE),vinylidene polyfluoride (PVDF), polyamide (PA), polypropylene (PP),nitrile rubber (NBR), chloroprene (CR), chlorofluorocarbons (FKM),and/or composite materials, including composite materials comprisingcarbon fibers, glass fibers, and/or aramid fibers.

The exhaust storage vessel 450 may be designed to maintain an internalpressure of about 1 bar to about 30 bar, an internal pressure of about10 bar to about 30 bar, an internal pressure of about 10 bar to about 15bar, an internal pressure of about 15 bar to about 27 bar, an internalpressure of about 20 bar to about 27 bar. The vessel may be designed toleak or vent before burst. The vessel may further comprise a pressurerelief device operably connected to the vessel and configured to reducepressure within the vessel. Examples of a pressure relief deviceinclude, but are not limited to, a pressure relief valve and a rupturedisc.

The vehicle 500 may further comprise a pressurizing device operablyconnected to the exhaust storage vessel 450 and configured to maintainpressure within the exhaust storage vessel 450. Examples of apressurizing device include a moveable press integrated with the vessel,wherein the moveable press is configured to maintain pressure within thevessel. For example, the moveable press may include, but is not limitedto, a hydraulic press or an electromagnetically activated press. Inother examples, the pressurizing device may comprise a compressor.Examples of a compressor include, but are not limited to, a centrifugalcompressor, a mixed-flow compressor, an axial-flow compressor, areciprocating compressor, a rotary screw compressor, a rotary vanecompressor, a scroll compressor, and a diaphragm compressor.

Vehicle 500 may further comprise a pressure monitoring device operablyconnected to the exhaust storage vessel 450 and configured to monitor aninternal pressure of the exhaust storage vessel 450. The pressuremonitoring device may comprise a piezoresistive strain gauge, acapacitive sensor, an electromagnetic sensor, a piezoelectric sensor, anoptical sensor, a potentiometric sensor, a thermal conductivity sensor,and/or an ionization sensor.

The vehicle 500 may further comprise a temperature monitoring systemconfigured to monitor the internal temperature of the exhaust storagevessel 450. The temperature monitoring system may comprise a thermostat,a thermistor, a thermocouple, and/or a resistive temperature detector.

The vehicle 500 may further comprise a control system configured tomonitor both pressure and temperature of the exhaust storage vessel 450and configured to regulate at least one of pressure and temperature inorder to maintain the carbon dioxide clathrate within a clathratestability range.

Without further elaboration, it is believed that one skilled in the artcan use the preceding description to utilize the invention to itsfullest extent. The claims and embodiments disclosed herein are to beconstrued as merely illustrative and exemplary, and not a limitation ofthe scope of the present disclosure in any way. It will be apparent tothose having ordinary skill in the art, with the aid of the presentdisclosure, that changes may be made to the details of theabove-described embodiments without departing from the underlyingprinciples of the disclosure herein. In other words, variousmodifications and improvements of the embodiments specifically disclosedin the description above are within the scope of the appended claims.The scope of the invention is therefore defined by the following claims.

The invention claimed is:
 1. A vehicle with reduced emissions, thevehicle comprising: a fuel storage vessel configured to store gasclathrates; a separation system operably connected to the fuel storagevessel and configured to dissociate the gas clathrates into a first hostmaterial and at least one gas; an engine operably connected to theseparation system and configured to utilize the at least one gas asfuel; a clathrate formation system operably connected to the engine andconfigured to combine an exhaust stream from the engine with a secondhost material to form carbon dioxide clathrates, wherein the exhauststream comprises carbon dioxide; and an exhaust storage vessel operablyconnected to the clathrate formation system and configured to storecarbon dioxide clathrates.
 2. The vehicle of claim 1, wherein the fuelstorage vessel is configured to receive the at least one gas and thefirst host material and form the gas clathrates within the fuel storagevessel.
 3. The vehicle of claim 1, wherein the fuel storage vessel isconfigured to be detachable and reattachable from the remainder of thevehicle.
 4. The vehicle of claim 3, wherein the fuel storage vessel isconfigured to be exchanged with a different fuel storage vessel that hasbeen pre-filled with gas clathrates.
 5. The vehicle of claim 1, whereinthe separation system comprises a separation vessel operably connectedto the fuel storage vessel.
 6. The vehicle of claim 5, wherein thevehicle further comprises a transport device operably connected to thefuel storage vessel and operably connected to the separation vessel andconfigured to transfer gas clathrates from the fuel storage vessel tothe separation vessel.
 7. The vehicle of claim 6, wherein the transportdevice is at least partially integrated into a portion of a surface ofthe fuel storage vessel.
 8. The vehicle of claim 6, wherein thetransport device comprises a pump.
 9. The vehicle of claim 8, whereinthe pump is a peristaltic pump.
 10. The vehicle of claim 8, wherein thepump is a screw pump.
 11. The vehicle of claim 5, wherein the separationsystem is configured to control the rate of dissociation of the gasclathrates by regulating at least one of the temperature and thepressure of the gas clathrates within the separation vessel.
 12. Thevehicle of claim 5, wherein the separation vessel is designed to ventbefore burst.
 13. The vehicle of claim 5, wherein the separation vesselis designed to leak before burst.
 14. The vehicle of claim 1, whereinthe separation system is integrated with the fuel storage vessel and theseparation system is configured to control the rate of dissociation ofthe gas clathrates by regulating at least one of the temperature and thepressure of the gas clathrates within the fuel storage vessel.
 15. Thevehicle of claim 1, further comprising a transport device configured totransport the dissociated at least one gas from the separation system tothe engine, wherein the transport device is operably connected to theseparation system and to the engine.
 16. The vehicle of claim 1, whereinthe separation system is configured to control the rate of dissociationof the gas clathrates based on fuel requirements of the engine.
 17. Thevehicle of claim 1, wherein the clathrate formation system is configuredto control the pressure and temperature of the exhaust stream and thesecond host material sufficient to form carbon dioxide clathrates withcarbon dioxide and the second host material.
 18. The vehicle of claim17, wherein the clathrate formation system comprises a cooling systemconfigured to cool the exhaust stream.
 19. The vehicle of claim 17,wherein the clathrate formation system comprises a pressurizationsystem.
 20. The vehicle of claim 17, wherein the clathrate formationsystem comprises a formation vessel operably connected to the exhauststorage vessel.
 21. The vehicle of claim 20, further comprising a carbondioxide removal system configured to separate carbon dioxide from theexhaust stream and deliver the removed carbon dioxide to the formationvessel.
 22. The vehicle of claim 21, wherein the carbon dioxide removalsystem comprises a removal vessel operably connected to the exhauststream and the formation vessel.
 23. The vehicle of claim 22, whereinthe removal vessel is configured to contact the exhaust stream with atleast one separation fluid.
 24. The vehicle of claim 22, wherein theremoval vessel is configured to contact the exhaust stream with analkali carbonate.
 25. The vehicle of claim 22, wherein the removalvessel comprises a membrane configured to separate carbon dioxide fromthe exhaust stream.
 26. The vehicle of claim 20, wherein the clathrateformation system is configured to control the rate of formation of thecarbon dioxide clathrates by regulating at least one of the temperatureand the pressure of exhaust gases within the formation vessel.
 27. Thevehicle of claim 17, wherein the clathrate formation system isintegrated with the exhaust storage vessel and the clathrate formationsystem is configured to form carbon dioxide clathrates by regulating atleast one of the temperature and the pressure of carbon dioxide and thesecond host material within the exhaust storage vessel to be compatiblewith forming carbon dioxide clathrates.
 28. The vehicle of claim 1,wherein the exhaust storage vessel is configured for removal of storedcarbon dioxide from the vehicle when the vehicle is otherwise not inuse.
 29. The vehicle of claim 1, further comprising a dissociation tankoperably connected to the exhaust storage vessel and configured toreceive carbon dioxide clathrates from the exhaust storage vessel. 30.The vehicle of claim 1, wherein the exhaust storage vessel is configuredto be detachable and reattachable from the remainder of the vehicle. 31.The vehicle of claim 30, wherein the exhaust storage vessel isconfigured to be exchanged with a different exhaust storage vessel thathas been emptied of carbon dioxide clathrates.
 32. The vehicle of claim1, further comprising a recycle system configured to transferdissociated host material from the separation system to the clathrateformation system.
 33. The vehicle of claim 1, wherein at least a portionof the first host material used to store gas clathrates is reused as thesecond host material to form carbon dioxide clathrates.